KR20230152121A - Resin composition, cured product, laminate, method for producing cured product, and semiconductor device - Google Patents

Abstract

A resin composition comprising a cyclized resin or a resin that is its precursor, and compound B represented by formula (1-1), a cured product obtained by curing the resin composition, a laminate comprising the cured product, and a method for producing the cured product. , and, a semiconductor device including the cured product or the laminate; X ¹ represents an n-valent ^linking group containing an aromatic ring structure, at least one of the bonding sites ^with the nitrogen atom in the formula for represents a group ^, R ¹ may ^{combine with} represents an integer of 1 or more, and m represents an integer of 1 or more.

Description

Resin composition, cured product, laminate, method for producing cured product, and semiconductor device

The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.

Cyclized resins such as polyimide are excellent in heat resistance and insulation, and are therefore applied to a variety of applications. The above uses are not particularly limited, but include, for example, semiconductor devices for mounting, use as an insulating film or sealant material, or as a protective film. Additionally, it is also used as a base film or cover lay for flexible substrates.

For example, in the above-mentioned use, cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.

Such a resin composition can be applied to a substrate, for example, by coating to form a photosensitive film, and then, as necessary, exposed, developed, heated, etc., to form a cured product on the substrate. there is.

The precursor of the cyclized resin, such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin, such as polyimide, in the cured product.

Since the resin composition can be applied by known application methods, etc., it can be said to have excellent manufacturing adaptability, such as, for example, a high degree of freedom in designing the shape, size, and application location of the applied resin composition. there is. In addition to the high performance of cyclized resins such as polyimide, and from the viewpoint of excellent manufacturing adaptability, industrial applications of the above-mentioned resin compositions are increasingly expected.

For example, in Patent Document 1, (a) alkali-soluble polyimide and/or alkali-soluble polyimide precursor, (b) a polymerizable compound having a block isocyanate structure and an unsaturated bond, (c) a photopolymerization initiator, and (d) A photosensitive resin composition containing a thermal crosslinking agent is described.

Patent Document 2 includes polyesteramide acid (A), an epoxy compound (B) having a fluorene skeleton, a urethane compound (C) having a double bond, a photopolymerization initiator (D), and a silane coupling agent (F). A photosensitive composition comprising a is described.

Patent Document 1: Japanese Patent Publication No. 2009-009107 Patent Document 2: Japanese Patent Publication No. 2019-139091

In a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin, the resulting cured product is required to have excellent chemical resistance.

The present invention relates to a resin composition from which a cured product with excellent chemical resistance can be obtained, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the cured product or the laminate. The purpose is to provide a semiconductor device including a semiconductor device.

Examples of representative embodiments of the present invention are shown below.

<1> Cyclized resin or a resin that is its precursor, and,

A resin composition containing compound B represented by formula (1-1).

[Formula 1]

X ¹ represents an n-valent ^linking group containing an aromatic ring structure, at least ^one of the bonding sites with the nitrogen atom in the formula for represents a group ^, R ¹ may ^{combine with} represents an integer of 1 or more, and m represents an integer of 1 or more.

<2> The resin composition according to <1>, wherein the content of the compound B relative to the total mass of the resin composition is 1% by mass or more.

<3> The resin composition according to <1> or <2>, further comprising a polymerizable compound different from the compound B.

<4> The resin composition according to <3>, wherein the content of the polymerizable compound is more than 0% by mass and 20% by mass or less, based on the total mass of the composition.

<5> The resin composition according to any one of <1> to <4>, wherein the acid value of the resin is 1 mmol/g or less.

<6> The resin composition according to any one of <1> to <5>, wherein the resin has a polymerizable group.

<7> The resin composition according to any one of <1> to <6>, wherein the molecular weight of the compound B is 1,000 or less.

<8> The resin composition according to any one of <1> to <7>, further comprising a polymerization initiator.

<9> The resin composition according to any one of <1> to <8>, wherein W ¹ in the formula (1-1) is a radical polymerizable group.

<10> The resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a redistribution layer.

<11> A cured product obtained by curing the resin composition according to any one of <1> to <10>.

<12> A laminate comprising two or more layers made of the cured material according to <11>, and including a metal layer between any one of the layers made of the cured material.

<13> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <10> to a substrate to form a film.

<14> The method for producing a cured product according to <13>, comprising an exposure step of exposing the film and a development step of developing the film.

<15> The method for producing a cured product according to <13> or <14>, comprising a heating step of heating the film at 50 to 450°C.

<16> A semiconductor device comprising the cured product according to <11> or the laminate according to <12>.

According to the present invention, a resin composition from which a cured product excellent in chemical resistance is obtained, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the cured product or the laminate A semiconductor device including a is provided.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.

In this specification, the numerical range indicated using the symbol “~” means a range that includes the numerical values written before and after “~” as the lower limit and upper limit, respectively.

In this specification, the term “process” is meant to include not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.

In the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include groups (atomic groups) that have substituents as well as groups (atomic groups) that do not have substituents. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

In this specification, “exposure” includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, the light used for exposure includes active light or radiation such as the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.

In this specification, “(meth)acrylate” means both “acrylate” and “methacrylate”, or “(meth)acrylate” means “acrylic” and “methacrylate”. "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".

In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, total solid content refers to the total mass of components excluding the solvent from all components of the composition. In addition, in this specification, solid content concentration refers to the mass percentage of other components excluding the solvent with respect to the total mass of the composition.

In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM- It can be obtained by connecting M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Co., Ltd.) in series. Unless otherwise specified, their molecular weights are assumed to be measured using THF (tetrahydrofuran) as an eluent. However, in cases where THF is not suitable as an eluent, such as when solubility is low, NMP (N-methyl-2-pyrrolidone) may be used. In addition, detection in GPC measurement is assumed to be performed using a UV ray (ultraviolet ray) detector with a wavelength of 254 nm, unless otherwise specified.

In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower," it refers to the reference layer among the plurality of layers in focus. There may be another layer on the top or bottom. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. In addition, unless otherwise specified, the direction in which the layers are laminated with respect to the substrate is referred to as "up", or, in the case where there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up", The opposite direction is called “down.” In addition, such setting of the vertical direction is for convenience in this specification, and in actual embodiments, the “up” direction in this specification may be different from vertically upward.

In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.

In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50%RH.

In this specification, a combination of preferred aspects is a more preferred aspect.

(Resin composition)

The resin composition of the present invention contains a cyclized resin or a resin that is its precursor, and compound B represented by formula (1-1).

[Formula 2]

X ¹ represents an n-valent ^linking group containing an aromatic ring structure, at least one of the bonding sites ^with the nitrogen atom in the formula for represents a group ^, R ¹ may ^{combine with} represents an integer of 1 or more, and m represents an integer of 1 or more.

The resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used to form a film to be subjected to exposure and development using a developer containing an organic solvent.

The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer.

In addition, the resin composition of the present invention may be used to form a photosensitive film used for positive development, or may be used to form a photosensitive film used for negative development, but it is not used for forming a photosensitive film used for negative development. desirable.

In the present invention, negative development refers to a phenomenon in which a non-exposed part is removed by development during exposure and development, and positive development refers to a phenomenon in which an exposed part is removed by development.

Examples of the exposure method, the developer solution, and the development method include the exposure method described in the exposure process in the explanation of the method for producing a cured product described later, the developer solution, and the development method described in the development process. This is used.

According to the resin composition of the present invention, a cured product excellent in chemical resistance is obtained.

Although the mechanism by which the above effect is obtained is unclear, it is assumed as follows.

Conventionally, a cured product has been obtained using a composition containing a cyclized resin or its precursor and a polymerizable compound.

The present inventors found that, in the present invention, chemical resistance is improved by using a polymerizable compound with a specific structure as the polymerizable compound.

This is because Compound B, which has a urethane bond and a polymerizable group, is included in the polymer, and hydrogen bonds are formed between the urethane bonds in the polymer, or between the urethane bond and the imide or amide site in the polymer. I guess.

In addition, it is believed that the resulting cured film has excellent breaking elongation because the polymer contains a urethane bond that has a soft structure compared to the imide ring structure.

In addition, the polymer contains a urethane bond, which has a soft structure compared to the imide ring structure, etc., thereby lowering the elastic modulus of the resulting cured film, reducing the internal stress during formation of the cured film, and suppressing bending of the cured film. .

Here, Patent Documents 1 and 2 do not describe the use of compound B.

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

<Specific resin>

The resin composition of the present invention contains at least one type of resin (specific resin) selected from the group consisting of cyclized resins and their precursors.

The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.

In the present invention, the main chain refers to the relatively longest bond chain among resin molecules.

Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide.

The precursor of a cyclized resin refers to a resin that becomes a cyclized resin by causing a change in its chemical structure due to an external stimulus. A resin that becomes a cyclized resin by causing a change in its chemical structure by heat is preferred, and a resin that becomes a cyclized resin by causing a change in its chemical structure by heat is preferred. A resin that becomes a cyclized resin by forming a ring structure is more preferable.

Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.

That is, the resin composition of the present invention contains, as a specific resin, at least one kind selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. It is preferable to include a resin (specific resin).

The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.

Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group.

When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, and more preferably contains a radical crosslinking agent described later. do. If necessary, a sensitizer described later may be further included. For example, a negative photosensitive film is formed from the resin composition of the present invention.

Additionally, the specific resin may have a polarity converter such as an acid-decomposable group.

When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. From the resin composition of the present invention, for example, a chemically amplified positive photoresist film or a negative photoresist film is formed.

When a specific resin has a polymerizable group, it is preferable that the resin also has a molecular chain containing a polymerizable group and a urea bond.

The molecular chain is preferably bonded to the main chain of the resin as a side chain, for example.

When a specific resin contains a repeating unit represented by formula (2) described later, the molecular chain is, for example, R ¹¹¹ , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ in the repeating unit represented by formula (2) It is desirable to include at least one of the following.

When a specific resin contains a repeating unit represented by formula (4) described later, the molecular chain is, for example, contained in at least one of R ¹³¹ and R ¹³² in the repeating unit represented by formula (4) It is desirable.

When a specific resin contains a repeating unit represented by formula (3) described later, the molecular chain is, for example, R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in the repeating unit represented by formula (3) It is desirable to include at least one of the following.

When a specific resin contains a repeating unit represented by the formula (X) described later, the molecular chain is, for example, contained in at least one of R ¹³³ and R ¹³⁴ in the repeating unit represented by the formula (X) It is desirable.

When a specific resin contains a repeating unit represented by the formula (PAI-2) described later, the molecular chain is, for example, R ¹¹¹ , R ¹¹⁷ and R in the repeating unit represented by the formula (PAI-2) It is desirable to include at least one of ¹¹³ .

When a specific resin contains a repeating unit represented by the formula (PAI-3) described later, the molecular chain is, for example, at least R ¹¹¹ and R ¹¹⁷ in the repeating unit represented by the formula (PAI-3). It is desirable to be included in one.

From the viewpoint of chemical resistance, the acid value of the specific resin is preferably 0 mmol/g to 1.0 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, and even more preferably 0 mmol/g to 0.6 mmol/g. desirable.

The acid value is measured, for example, by the method described in JIS K 0070:1992.

Since a low-oxidation resin with an acid value within the above range has high alkali permeability, a cured film using such a resin is unlikely to be damaged by an alkaline chemical solution (for example, tetramethylammonium hydroxide, etc.).

In addition, by using compound B, hydrogen bonds are formed between urethanes or between urethanes and imides in the resin in the cured film, so the organic solvent (for example, DMSO, etc.) in the cured film is formed. It is thought that the infiltration of

From the above, it is assumed that chemical resistance is improved by the combination of compound B with a resin whose acid value is within the above range. That is, by using a resin having an acid value within the above range in combination with Compound B in a resin composition, the resulting cured film becomes less susceptible to damage by alkali or organic solvents contained in developers, etc., and alkali or organic solvents contained in other compositions. I think so.

[Polyimide precursor]

The polyimide precursor used in the present invention is not particularly defined in its type, but preferably contains a repeating unit represented by the following formula (2).

[Formula 3]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or -NH-, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, R ¹¹³ and R ¹¹⁴ each independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² in formula (2) each independently represent an oxygen atom or -NH-, and the oxygen atom is preferable.

R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing a straight-chain or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, including a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, and a cyclic aliphatic group with 3 to 20 carbon atoms. A group consisting of ~20 aromatic groups or a combination thereof is preferable, and a group containing an aromatic group with 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reducing hydrocarbon group substituted with a group containing a hetero atom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- are exemplified, and groups represented by -Ar-L-Ar- are particularly preferred. However, Ar is each independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, - SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. These preferable ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.

Specifically, it is preferable that it is a diamine containing a straight-chain or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, It is more preferable that it is diamine containing an aromatic group of 6 to 20 carbon atoms. The straight-chain or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a reducing hydrocarbon group substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

[Formula 4]

In the formula, A represents a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -C(=O)-, -S- , -SO ₂ -, -NHCO-, or a combination thereof is preferably a group selected from a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (= It is more preferable that it is a group selected from O)-, -S-, or -SO ₂ -, -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, Or, -C(CH ₃ ) ₂ - is more preferable.

In the formula, * represents a binding site with another structure.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohex. three; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane phosphorus and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl Ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenylsulfone, 4,4'- or 3,3'-di Aminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2, 2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) ) Sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diamino paraterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy) )Benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1 ,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3' -Dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminoctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3',4,4'-tetra Aminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4 '-Diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5' -Tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3 , 5,6-Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl) )Octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1 ,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1, 5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-di Methylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino -2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoro) Romethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoc Si) diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4 ,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluoro At least one type of diamine selected from tolidine and 4,4'-diaminoquaterphenyl can be mentioned.

Additionally, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.

Moreover, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are also preferably used.

R ¹¹¹ is preferably represented as -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film. However, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or - NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

In addition, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or (61) from the viewpoint of i-line transmittance. In particular, from the viewpoint of i-line transmittance and ease of availability, it is more preferable that it is a divalent organic group represented by formula (61).

Equation (51)

[Formula 5]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, * each independently represents a bonding site with a nitrogen atom in formula (2).

Examples of the monovalent organic group for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group with 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. You can.

[Formula 6]

In formula (61), R ⁵⁸ and R ⁵⁹ each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom in formula (2).

As diamines that give the structure of formula (51) or (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2 ,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used singly or in combination of two or more types.

Moreover, from the viewpoint of chemical resistance of the cured film obtained, it is preferable that R ¹¹¹ is a group represented by the following formula (R-1).

[Formula 7]

In formula (R-1), Ar ¹ to Ar ³ each independently represent an aryl group, and * each represents a bonding site with a nitrogen atom in formula (2).

In formula (R-1), Ar ¹ and Ar ³ are each independently preferably an aromatic hydrocarbon group, more preferably a phenylene group, and still more preferably a 1,4-phenylene group. Ar ¹ and Ar ³ may each independently be an aromatic heterocycle. Examples of heteroatoms contained in the aromatic heterocycle include oxygen atom, sulfur atom, and nitrogen atom. Moreover, the aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.

In formula (R-1), Ar ² is preferably a group represented by the following formula (AR2-1).

[Formula 8]

In formula (AR2-1), * represents the binding site with Ar ¹ and Ar ³ in formula (R-1), respectively.

In addition, Ar ² also has the same contribution as Ar ¹ described above.

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.

In formula (5) or formula (6), * each independently represents a binding site with another structure.

[Formula 9]

In formula (5), R ¹¹² is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, It is preferably a group selected from -SO ₂ -, and -NHCO-, and combinations thereof, and is a single bond, an alkylene group having 1 to 3 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, and -S. It is more preferable that it is a group selected from - and -SO ₂ -, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and It is more preferable that it is a divalent group selected from the group consisting of -SO ₂ -.

R ¹¹⁵ specifically includes the tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. The polyimide precursor has a structure corresponding to R ¹¹⁵ and may contain only one type or two or more types of tetracarboxylic dianhydride residues.

Tetracarboxylic dianhydride is preferably represented by the following formula (O).

[Formula 10]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferable range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in formula (2), and the preferable range is also the same.

Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride. Water, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethe Intetracarboxylic dianhydride, 2,2',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4 '-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ',3,3'-Diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8 -Naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4- Dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of 1 to 6 carbon atoms thereof.

Additionally, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited as preferable examples.

In formula (2), it is possible for at least one of R ¹¹¹ and R ¹¹⁵ to have an OH group. More specifically, R ¹¹¹ may be a residue of a bisaminophenol derivative.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Moreover, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a block isocyanate group, and an amino group. As the radically polymerizable group included in the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.

Groups having an ethylenically unsaturated bond include vinyl group, allyl group, isoallyl group, 2-methylallyl group, group having an aromatic ring directly bonded to the vinyl group (for example, vinylphenyl group, etc.), (meth)acrylamide. Group, (meth)acryloyloxy group, group represented by the following formula (III), etc. are mentioned, and group represented by the following formula (III) is preferable.

[Formula 11]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferable.

In formula (III), * represents a binding site with another structure.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkyleneoxy group.

Suitable examples of R ²⁰¹ include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, and 1,2-butanediyl group. , 1,3-butanediyl group, -CH ₂ CH(OH)CH ₂ -, polyalkyleneoxy group, alkylene groups such as ethylene group and propylene group, -CH ₂ CH(OH)CH ₂ - , cyclohexyl group, and polyalkyleneoxy group are more preferable, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy group are more preferable.

In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.

When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an alternating arrangement, etc. It may be an array with a pattern.

The carbon number of the alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5. It is more preferable, it is still more preferable that it is 2-4, it is especially preferable that it is 2 or 3, and it is most preferable that it is 2.

Moreover, the alkylene group may have a substituent. Preferred substituents include an alkyl group, an aryl group, and a halogen atom.

Moreover, the number of alkyleneoxy groups (repeating number of polyalkyleneoxy groups) contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.

As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, or a combination of a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups. group is preferred, polyethyleneoxy group or polypropyleneoxy group is more preferred, and polyethyleneoxy group is more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged to form a block, or may be arranged in an alternating pattern or the like. The preferred embodiments of the repeating number of the ethyleneoxy group and the like in these groups are as described above.

In Formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a counterpart salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity converter such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes under the action of acid to generate alkali-soluble groups such as phenolic hydroxy groups and carboxy groups, but includes acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl groups. An ester group or the like is preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.

Specific examples of acid-decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, and tert-view. Toxycarbonylmethyl group, trimethylsilyl ether group, etc. can be mentioned. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group is preferable.

Moreover, it is preferable that the polyimide precursor also has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and is preferably 20 mass% or less.

Additionally, for the purpose of improving adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by the formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further broaden the width of the exposure latitude.

Equation (2-A)

[Formula 12]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom. Alternatively, it represents a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and their preferred ranges are also the same. do.

R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferable range is also the same.

The polyimide precursor may contain one type of repeating unit represented by Formula (2), or may contain two or more types. Moreover, it may contain a structural isomer of the repeating unit represented by formula (2). Moreover, it goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, an aspect in which the content of the repeating unit represented by Formula (2) is 50 mol% or more of all repeating units is mentioned. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor except the terminal may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.

The molecular weight dispersion degree of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyimide precursor is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable.

In this specification, the dispersion of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.

Moreover, when the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion degree calculated from the plurality of types of polyimide precursors as one resin are respectively within the above ranges.

[polyimide]

The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component.

In this specification, alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23°C with respect to 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and from the viewpoint of pattern formation, it is a polyimide that dissolves 0.5 g or more. It is preferable, and it is more preferable that it is a polyimide that dissolves 1.0 g or more. The upper limit of the amount dissolved is not particularly limited, but is preferably 100 g or less.

Moreover, it is preferable that the polyimide is a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film obtained.

In this specification, “main chain” refers to the relatively longest bond chain among the molecules of the polymer compound constituting the resin, and “side chain” refers to other bond chains.

-Fluorine atom-

From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide also has a fluorine atom.

The fluorine atom is preferably included, for example, in R ¹³² in the repeating unit represented by formula (4) described later, or R ¹³¹ in the repeating unit represented by formula (4) described later, and It is more preferable that R ¹³² in the repeating unit represented by formula (4) or R ¹³¹ in the repeating unit represented by formula (4) described later be included as a fluorinated alkyl group.

The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5 mass% or more, and is preferably 20 mass% or less.

-Silicon Atom-

From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide also has silicon atoms.

The silicon atom is preferably included, for example, in R ¹³¹ in the repeating unit represented by formula (4) described later, and an organic modification described later in R ¹³¹ in the repeating unit represented by formula (4) described later. It is more preferable to include it as a (poly)siloxane structure.

In addition, the silicon atom or the organic modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.

The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass% or more, and more preferably 20 mass% or less.

-Ethylenically unsaturated bond-

From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds.

The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have it at the side chain, but it is preferable to have it at the side chain.

The ethylenically unsaturated bond preferably has radical polymerization.

The ethylenically unsaturated bond is preferably included in R ¹³² in the repeating unit represented by formula (4) described later, or R ¹³¹ in the repeating unit represented by formula (4) described later, and is represented by the formula (4) described later: It is more preferable that R ¹³² in the repeating unit represented by 4) or R ¹³¹ in the repeating unit represented by formula (4) described later be included as a group having an ethylenically unsaturated bond.

Among these, the ethylenically unsaturated bond is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and the ethylenic unsaturated bond is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later. It is more preferable to include it as a group having a bond.

Examples of groups having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, Groups represented by the following formula (IV), etc. can be mentioned.

[Formula 13]

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and a hydrogen atom or a methyl group is preferable.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, (poly) alkyleneoxy group having 2 to 30 carbon atoms (the carbon number of the alkylene group is preferably 2 to 12, more preferably 2 to 6, and especially preferably 2 or 3; the number of repeats is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a combination of 2 or more thereof.

Additionally, the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or combinations thereof.

As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

[Formula 14]

In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group combining two or more thereof, and X represents an oxygen atom or sulfur. represents an atom, * represents a bonding site with another structure, and ● represents a bonding site with an oxygen atom where R ²¹ in formula (IV) is bonded.

In formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms for L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is 2 carbon atoms for R ²¹ described above. It is the same as the preferred embodiment of an alkylene group of ~12 or a (poly)alkyleneoxy group of 2-30 carbon atoms.

In formula (R1), X is preferably an oxygen atom.

In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiments are also the same.

The structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanate It is obtained by reacting itoethyl methacrylate, etc.).

The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.) Lose.

The structure represented by formula (R3) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate) etc.) is obtained by reacting.

In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.

The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-Polymerizable groups other than groups having ethylenically unsaturated bonds-

The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond.

Examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.

Polymerizable groups other than the group having an ethylenically unsaturated bond are preferably included, for example, in R ¹³¹ in the repeating unit represented by formula (4) described later.

The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polarity Converter-

Polyimide may have a polarity converter such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group demonstrated for R ¹¹³ and R ¹¹⁴ in the above-mentioned formula (2), and the preferred embodiment is also the same.

The polarity converter is contained, for example, at R ¹³¹ , R ¹³² in the repeating unit represented by the formula (4) described later, and at the terminal of the polyimide.

-Sanga-

When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more.

Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.

In addition, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH. /g is more preferable, and 5 to 20 mgKOH/g is more preferable.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

From the viewpoint of chemical resistance, the acid value of the polyimide is preferably 0 mmol/g to 1.0 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, and even more preferably 0 mmol/g to 0.6 mmol/g. desirable.

Moreover, as an acidic group contained in a polyimide, from a viewpoint of both storage stability and developability, the acidic group whose pKa is 0-10 is preferable, and the acidic group whose pKa is 3-8 is more preferable.

pKa refers to a dissociation reaction in which hydrogen ions are released from an acid, and the equilibrium constant Ka is expressed by the negative common logarithm pKa. In this specification, unless otherwise specified, pKa is a value calculated by ACD/ChemSketch (registered trademark). Alternatively, you may refer to the values published in the "Revised 5th Edition Chemical Handbook Basics" edited by the Japanese Chemical Society.

In addition, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.

As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxyl group-

From the viewpoint of ensuring an appropriate development speed using an alkaline developer, it is preferable that the polyimide has a phenolic hydroxy group.

The polyimide may have a phenolic hydroxy group at the end of the main chain or may have a phenolic hydroxy group at the side chain.

The phenolic hydroxy group is preferably included in, for example, R ¹³² in the repeating unit represented by Formula (4) described later, or R ¹³¹ in the repeating unit represented by Formula (4) described later.

The amount of phenolic hydroxy groups relative to the total mass of polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4).

[Formula 15]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

When it has a polymerizable group, the polymerizable group may be located at least one of R ¹³¹ and R ¹³² and may be located at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2).

Equation (4-1)

[Formula 16]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same meaning as in formula (4).

Equation (4-2)

[Formula 17]

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

Examples of the polymerizable group include groups containing the above-mentioned ethylenically unsaturated bond, or crosslinkable groups other than groups containing the above-mentioned ethylenically unsaturated bond.

R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include those similar to R ¹¹¹ in formula (2), and the preferable range is also the same.

Additionally, R ¹³¹ includes a diamine residue remaining after removal of the amino group of diamine. Examples of diamine include aliphatic, cyclic aliphatic, or aromatic diamine. As a specific example, an example of R ¹¹¹ in formula (2) of the polyimide precursor can be given.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warping during firing. More preferably, it is a diamine residue containing two or more of either an ethylene glycol chain or a propylene glycol chain in one molecule, and even more preferably it is a diamine residue containing the above diamine and does not contain an aromatic ring. It’s Min Zangi.

Diamines containing two or more of either or both ethylene glycol chains and propylene glycol chains in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name above, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy) Toxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc. are mentioned, but are not limited to these. .

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, the same thing as ^R115 in Formula (2) is exemplified, and the preferable range is also the same.

For example, four bonds of a tetravalent organic group exemplified by R ¹¹⁵ are combined with four -C(=O)- moieties in the above formula (4) to form a condensed ring.

In addition, R ¹³² includes the tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. As a specific example, an example of R ¹¹⁵ in formula (2) of the polyimide precursor can be given. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, (DA-1)~( DA-18) can be cited as a preferable example, and as R ¹³² , the above (DAA-1) to (DAA-5) can be cited as more preferable examples.

Moreover, it is preferable that the polyimide also has a fluorine atom in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and is preferably 20% by mass or less.

Additionally, for the purpose of improving adhesion to the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

Additionally, in order to improve the storage stability of the resin composition, the main chain terminals of the polyimide are preferably sealed with an end capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Among these, it is more preferable to use monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8-hydroxy. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2 -Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid , 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol , 4-aminothiophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more types of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

-Imidization rate (closing rate)-

The imidization ratio (also referred to as "closing ratio") of polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more from the viewpoint of the film strength and insulation properties of the resulting organic film. .

The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

The imidation rate is measured, for example, by the following method.

The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 around 1377 cm ^-1 , which is the absorption peak derived from the imide structure, is determined. Next, after heat treating the polyimide at 350°C for 1 hour, the infrared absorption spectrum is measured again and the peak intensity P2 around 1377 cm ^-1 is determined. Using the obtained peak intensities P1 and P2, the imidation rate of the polyimide can be determined based on the following formula.

Imidization rate (%) = (peak intensity P1/peak intensity P2) x 100

The polyimide may contain repeating units represented by the above formula (4), all of which contain one type of R ¹³¹ or R ¹³² , or a repeating unit represented by the above formula (4) containing two or more different types of R ¹³¹ or R ¹³² . ) may be included. In addition, the polyimide may also contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include repeating units expressed by the above-mentioned formula (2).

Polyimide can be prepared, for example, by reacting tetracarboxylic dianhydride with diamine (part of it replaced with a monoamine end cap) at low temperature, or by reacting tetracarboxylic dianhydride (part with acid anhydride or monoacid chloride compound or A method of reacting diamine with a mono-active ester compound (substituted with an end capping agent, which is a monoamine) to obtain a diester using tetracarboxylic dianhydride and an alcohol, and then using diamine (partially replaced with an end capping agent that is a monoamine) and a condensing agent. A method of reacting in the presence of a diester using tetracarboxylic dianhydride and an alcohol, then acid chloridating the remaining dicarboxylic acid and reacting it with diamine (part of which is replaced with a monoamine end cap agent), etc. A method of obtaining a polyimide precursor and completely imidizing it using a known imidization reaction method, or a method of stopping the imidization reaction midway and introducing a partial imide structure, furthermore, It can be synthesized using a method of introducing a partial imide structure by blending a fully imidized polymer and its polyimide precursor. Additionally, other known polyimide synthesis methods can also be applied.

The weight average molecular weight (Mw) of polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.

Moreover, the number average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.

The molecular weight dispersion degree of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of polyimide is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable.

Moreover, when the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polyimide are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion degree calculated from the plurality of types of polyimides as one resin are respectively within the above ranges.

[Polybenzoxazole precursor]

The polybenzoxazole precursor used in the present invention is not particularly defined in terms of its structure, etc., but preferably contains a repeating unit represented by the following formula (3).

[Formula 18]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ each have the same meaning as R ¹¹³ in formula (2), and their preferable ranges are also the same. That is, it is preferable that at least one of the groups is a polymerizable group.

In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a straight-chain aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, dicarboxylic acid containing an aliphatic group and dicarboxylic acid residue containing an aromatic group are preferable, and dicarboxylic acid residue containing an aromatic group is more preferable.

As dicarboxylic acids containing aliphatic groups, dicarboxylic acids containing a straight-chain or branched (preferably straight-chain) aliphatic group are preferable, and dicarboxylic acids consisting of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH are more preferred. desirable. The carbon number of the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, more preferably 3 to 20, and even more preferably 4 to 15. , it is particularly preferable that it is 5 to 10. It is preferable that the linear aliphatic group is an alkylene group.

As dicarboxylic acids containing a straight-chain aliphatic group, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2 -Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2, 2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecane diacid, tridecane Caine diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecane diacid, nonadecane diacid, icosane diacid, henicosein diacid, dococein diacid, trichocein diacid, tetracocein diacid, pentacocein diacid, hexacocein diacid, heptacocein diacid, octacocein diacid, nonacosein diacid, triacontaine diacid, hentriacontain diacid, dotriacontane diacid, diglye Cholic acid, dicarboxylic acid represented by the formula below, etc. can be mentioned.

[Formula 19]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As dicarboxylic acid containing an aromatic group, dicarboxylic acid having the following aromatic group is preferable, and dicarboxylic acid consisting only of the group having the following aromatic group and two -COOH is more preferable.

[Formula 20]

In the formula, A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - represents a divalent group selected from the group consisting of, and * each independently represents a binding site with another structure.

Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxy diphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R ¹¹⁵ in the above formula (2), and its preferable range is also the same.

R ¹²² is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4 ,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3' -Dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-( 3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxy Phenyl) methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-di Amino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxy Diphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihyde Roxybenzene, etc. can be mentioned. These bisaminophenols may be used individually or in mixture.

Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic group are preferred.

[Formula 21]

_{In the formula , _} Indicates the binding site. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Moreover, R ¹²² is preferably also a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of a total of four * and # are bonding sites with the nitrogen atom to which R 122 in formula (3) is bonded, and the other two are bonding sites with the nitrogen atom to which R ¹²² is bonded in formula (3). ) is preferably a bonding site with the oxygen atom to which R ¹²² is bonded, two * are bonding sites with the oxygen atom to which R ¹²² is bonded in formula (3), and two # are bonding sites with the oxygen atom to which R 122 is bonded in formula (3) is a bonding site with the nitrogen atom to which R ¹²² is bonded, or two * are bonding sites with the nitrogen atom to which R ¹²² in formula (3) is bonded, and two # are bonding sites with R in formula (3) It is more preferable that ¹²² is a bonding site with the oxygen atom to which 122 is bonded, two * are bonding sites with the oxygen atom to which R ¹²² is bonded in formula (3), and two # are R in formula (3) It is more preferable that ¹²² is the binding site with the nitrogen atom to which it is bound.

The bisaminophenol derivative is also preferably a compound represented by the formula (A-s).

[Formula 22]

In formula (As), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, single bond, or the following formula (A- It is an organic group selected from the group sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

[Formula 23]

(In formula (A-sc), * represents bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the formula (A-s).)

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, that is, at R ₃ , is thought to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and when cured at low temperature, This is particularly preferable because the effect of increasing the cyclization rate is further increased.

Moreover, in the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group because the effects of high transparency to i-line and high cyclization rate when cured at low temperature can be maintained.

Moreover, in the above formula (As), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, especially -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) _2- is more preferable because it is possible to obtain a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and high cyclization rate when cured at low temperature. do.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs No. 0085 to 0094 and Example 1 (Paragraph No. 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506 can be referred to. , these contents are incorporated in this specification.

Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Laid-Open No. 2013-256506, the contents of which are incorporated herein by reference. Of course, it goes without saying that it is not limited to these.

In addition to the repeating unit of the formula (3), the polybenzoxazole precursor may also contain other types of repeating units.

The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit because it can suppress the occurrence of bending due to ring closure.

[Formula 24]

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R ^2s is a hydrocarbon group with 1 to 10 carbon atoms, R ^3s , At least one of R ^4s , R ^5s , and R ^6s is an aromatic group, and the others are hydrogen atoms or organic groups having 1 to 30 carbon atoms, and may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a+b.

In formula (SL), preferred examples of Z include those where R ^5s and R ^6s in the b structure are phenyl groups. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, thereby achieving both the effect of suppressing bending and the effect of improving solvent solubility.

When containing a diamine residue represented by the formula (SL) as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.

The molecular weight dispersion degree of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersion degree of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, 2.3 or less is still more preferable, and 2.2 or less is preferable. The following is even more preferable.

Moreover, when the resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polybenzoxazole precursor are within the above ranges. . Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion degree calculated from the plurality of types of polybenzoxazole precursors as one resin are respectively within the above ranges.

[polybenzoxazole]

The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and is a compound represented by the following formula (X) and has a polymerizable group. It is more desirable. As the polymerizable group, a radical polymerizable group is preferable. Moreover, the compound represented by the following formula (X) may be a compound having a polarity converter such as an acid-decomposable group.

[Formula 25]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

When having a polarity converter such as a polymerizable group or an acid-decomposable group, the polarity converter such as a polymerizable group or an acid-decomposable group may be located at least one of R ¹³³ and R ¹³⁴ , and may be represented by the following formula (X-1) or formula (X As shown in -2), it may be located at the terminal of polybenzoxazole.

Equation (X-1)

[Formula 26]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity converter such as a polymerizable group or an acid-decomposable group, and if it is not a polarity converter such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other group is an organic group. It has the same meaning as equation (X).

Equation (X-2)

[Formula 27]

In formula (X-2), R ¹³⁷ is a polarity converter such as a polymerizable group or an acid-decomposable group, other groups are substituents, and the other groups have the same meaning as in formula (X).

The polarity converter group, such as a polymerizable group or an acid-decomposable group, has the same meaning as the polymerizable group explained in the polymerizable group contained in the above-mentioned polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. Specific examples include R ¹²¹ in formula (3) of the polybenzoxazole precursor. Moreover, its preferred example is the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include R ¹²² in formula (3) of the polybenzoxazole precursor. Moreover, its preferred example is the same as R ¹²² .

For example, four bonds of a tetravalent organic group exemplified by R ¹²² are combined with a nitrogen atom and an oxygen atom in the formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. In the structures below, * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X), respectively.

[Formula 28]

The oxazolization rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolization by heating is reduced, and the occurrence of warping can be more effectively suppressed.

The oxazolization rate is measured, for example, by the following method.

The infrared absorption spectrum of polybenzoxazole is measured, and the peak intensity Q1 around 1650 cm ^-1 , which is the absorption peak derived from the amide structure of the precursor, is determined. Next, it is normalized by the absorption intensity of the aromatic ring visible around 1490 cm ^-1 . After heat treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, the peak intensity Q2 around 1650 cm ^-1 is determined, and the absorption intensity of the aromatic ring visible around 1490 cm ^-1 is normalized. Using the obtained standard values of peak intensities Q1 and Q2, the oxazolization rate of polybenzoxazole can be determined based on the following formula.

Oxazolization rate (%) = (standard value of peak intensity Q1/standard value of peak intensity Q2) × 100

^The polybenzoxazole ^{may contain} repeating units of the above formula ⁽ It may contain a repeating unit of X). In addition, polybenzoxazole may also contain other types of repeating units in addition to the repeating units of the formula (X).

Polybenzoxazole is produced, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichloride and dicarboxylic acid derivatives of the dicarboxylic acid, etc. It is obtained by obtaining a precursor and oxazolating it using a known oxazolation reaction method.

Additionally, in the case of dicarboxylic acid, in order to increase the reaction yield, etc., an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Moreover, when containing two or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is within the above range.

Moreover, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.

The molecular weight dispersion degree of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the molecular weight dispersion of polybenzoxazole is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, 2.3 or less is still more preferable, and 2.2 or less is preferable. is even more preferable.

Moreover, when the resin composition contains multiple types of polybenzoxazole as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polybenzoxazole are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are respectively within the above ranges.

[Polyamideimide precursor]

The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).

[Formula 29]

In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are connected by a single bond or linking group, A straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a combination of two or more of these by a single bond or linking group. One group is preferable, and an aromatic group with 6 to 20 carbon atoms, or a group in which two or more aromatic groups with 6 to 20 carbon atoms are combined by a single bond or linking group is more preferable.

The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group combining two or more thereof. , -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group combining two or more thereof is more preferable.

As the alkylene group, an alkylene group with 1 to 20 carbon atoms is preferable, an alkylene group with 1 to 10 carbon atoms is more preferable, and an alkylene group with 1 to 4 carbon atoms is still more preferable.

As the halogenated alkylene group, a halogenated alkylene group with 1 to 20 carbon atoms is preferable, a halogenated alkylene group with 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group with 1 to 4 carbon atoms is more preferable. do. Additionally, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferable. The halogenated alkylene group may have hydrogen atoms or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms are substituted with halogen atoms. Examples of a preferable halogenated alkylene group include (ditrifluoromethyl)methylene group.

As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Additionally, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the halogenation, chlorination is preferable.

In the present invention, a compound having three carboxyl groups is called a tricarboxylic acid compound.

Two of the three carboxyl groups of the tricarboxylic acid compound may be acid anhydride.

Examples of tricarboxylic acid compounds that may be halogenated used in the production of polyamideimide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.

These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, the tricarboxylic acid compound includes a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or, A tricarboxylic acid compound containing two or more groups combined by a bond or linking group is preferable, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group containing two or more aromatic groups having 6 to 20 carbon atoms combined by a single bond or linking group. Tricarboxylic acid compounds are more preferred.

Additionally, specific examples of tricarboxylic acid compounds include 1,2,3-propane tricarboxylic acid, 1,3,5-pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, and phthalic acid (or , phthalic anhydride) and benzoic acid are linked to a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, or a phenylene group. You can.

These compounds may be compounds in which two carboxyl groups are anhydrized (for example, trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride chloride).

In the formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ each have the same meaning as R ¹¹¹ , A ² , and R ¹¹³ in the above-mentioned formula (2), and their preferred embodiments are also the same.

The polyamideimide precursor may further include other repeating units.

Other repeating units include a repeating unit represented by the above-mentioned formula (2), a repeating unit represented by the following formula (PAI-1), and the like.

[Formula 30]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.

In formula (PAI-1), R ¹¹⁶ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are connected by a single bond or linking group, A straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a combination of two or more of these by a single bond or linking group. One group is preferable, and an aromatic group with 6 to 20 carbon atoms, or a group in which two or more aromatic groups with 6 to 20 carbon atoms are combined by a single bond or linking group is more preferable.

The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group combining two or more thereof. , -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group combining two or more thereof is more preferable.

As the alkylene group, an alkylene group with 1 to 20 carbon atoms is preferable, an alkylene group with 1 to 10 carbon atoms is more preferable, and an alkylene group with 1 to 4 carbon atoms is still more preferable.

As the halogenated alkylene group, a halogenated alkylene group with 1 to 20 carbon atoms is preferable, a halogenated alkylene group with 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group with 1 to 4 carbon atoms is more preferable. do. Additionally, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferable. The halogenated alkylene group may have hydrogen atoms or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms are substituted with halogen atoms. Examples of a preferable halogenated alkylene group include (ditrifluoromethyl)methylene group.

As the arylene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

Additionally, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.

In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound.

The carboxyl group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.

Examples of dicarboxylic acid compounds or dicarboxylic acid dihalide compounds that may be halogenated used in the production of polyamideimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. I can hear it.

These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include straight-chain aliphatic groups with 2 to 20 carbon atoms, branched aliphatic groups with 3 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, and 6 to 20 carbon atoms. A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing an aromatic group or a group of two or more thereof by a single bond or linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a group having 6 carbon atoms by a single bond or linking group is preferable. A dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a combination of two or more ~20 aromatic groups is more preferable.

Additionally, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2 -Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2- Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2 ,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentadecane diacid, hexadecane diacid, heptadecane diacid, octadecane diacid, nonadecane diacid, icosane diacid, henicosein diacid, dococein diacid, trichocein diacid, tetradecane diacid. Cosein diacid, Pentacocein diacid, Hexacocein diacid, Heptacocein diacid, Octacocein diacid, Nonacocein diacid, Triacontaine diacid, Hentriacontaine diacid, Dotriacontaine diacid, Diglycolic acid , phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxy diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. I can hear it.

Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxyl groups of the above-mentioned dicarboxylic acid compounds are halogenated.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2) described above, and the preferred embodiment is also the same.

Additionally, the polyamideimide precursor preferably also has a fluorine atom in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and is preferably 20 mass% or less.

Additionally, for the purpose of improving adhesion to the substrate, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, an embodiment in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. is used as the diamine component can be mentioned.

As an embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) An example of this is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and , it may be any one of the repeating units shown in equation (2).

Additionally, as another embodiment of the polyamideimide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is equal to the total content of all repeating units. An embodiment in which it is 50 mol% or more can be mentioned. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by the formula (PAI-2) or repeating units represented by the formula (PAI-1) Any one of these may be used.

The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. Moreover, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

The molecular weight dispersion degree of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamideimide precursor is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable. Moreover, when the resin composition contains multiple types of polyamideimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polyamideimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion degree calculated from the plurality of types of polyamideimide precursors as one resin are respectively within the above ranges.

[polyamideimide]

The polyamideimide used in the present invention may be alkali-soluble polyamideimide, or may be polyamideimide soluble in a developer containing an organic solvent as a main component.

In this specification, alkali-soluble polyamideimide refers to polyamideimide that dissolves 0.1 g or more at 23°C with respect to 100 g of 2.38% by mass tetramethylammonium aqueous solution. From the viewpoint of pattern formation, polyamideimide dissolves 0.5 g or more. It is preferable that it is amideimide, and it is more preferable that it is polyamideimide that dissolves 1.0 g or more. The upper limit of the amount dissolved is not particularly limited, but is preferably 100 g or less.

Moreover, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

-Fluorine atom-

From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamideimide has a fluorine atom.

For example, the fluorine atom is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and is included in the repeating unit represented by the formula (PAI-3) described later. It is more preferable that R ¹¹⁷ or R ¹¹¹ is included as an alkyl fluoride group.

The amount of fluorine atoms relative to the total mass of polyamideimide is preferably 5 mass% or more, and is preferably 20 mass% or less.

-Ethylenically unsaturated bond-

From the viewpoint of the film strength of the resulting organic film, polyamideimide may have ethylenically unsaturated bonds.

Polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferable to have it at the side chain.

The ethylenically unsaturated bond preferably has radical polymerization.

The ethylenically unsaturated bond is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later, and in the repeating unit represented by the formula (PAI-3) described later. It is more preferable that R ¹¹⁷ or R ¹¹¹ be included as a group having an ethylenically unsaturated bond.

The preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

The amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polymerizable groups other than ethylenically unsaturated bonds-

Polyamideimide may have polymerizable groups other than ethylenically unsaturated bonds.

Examples of the polymerizable groups other than the ethylenically unsaturated bond in polyamideimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the polyimide described above.

Polymerizable groups other than the ethylenically unsaturated bond are preferably included, for example, in R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later.

The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

-Polarity Converter-

Polyamideimide may have a polarity converter such as an acid-decomposable group. The acid-decomposable group in polyamideimide is the same as the acid-decomposable group explained for R ¹¹³ and R ¹¹⁴ in the above-mentioned formula (2), and the preferred embodiment is also the same.

-Sanga-

When polyamideimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. do.

Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.

In addition, when polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of polyamideimide is preferably 2 to 35 mgKOH/g, and is 3. ~30mgKOH/g is more preferred, and 5~20mgKOH/g is more preferred.

From the viewpoint of chemical resistance, the acid value of polyamideimide is preferably 0 mmol/g to 1.2 mmol/g, more preferably 0 mmol/g to 0.8 mmol/g, and 0 mmol/g to 0.6 mmol/g. It is more desirable.

The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

Moreover, as an acidic group contained in polyamideimide, the same group as the acidic group in the polyimide mentioned above can be mentioned, and the preferable aspect is also the same.

-Phenolic hydroxyl group-

From the viewpoint of ensuring an appropriate development speed using an alkaline developer, it is preferable that polyamideimide has a phenolic hydroxy group.

Polyamideimide may have a phenolic hydroxy group at the end of the main chain or may have a phenolic hydroxy group at the side chain.

The phenolic hydroxy group is preferably included in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by the formula (PAI-3) described later.

The amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

There is no particular limitation as to the polyamideimide used in the present invention as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3).

[Formula 31]

In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ each have the same meaning as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), and the preferred embodiments are also the same.

When it has a polymerizable group, the polymerizable group may be located at least one of R ¹¹¹ and R ¹¹⁷ , and may be located at the terminal of the polyamideimide.

In order to improve the storage stability of the resin composition, it is preferable to seal the main chain terminals of the polyamideimide with an end capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. The preferred embodiment of the end cap agent is the same as the preferred embodiment of the end cap agent for polyimide described above.

-Imidization rate (closing rate)-

The imidization ratio (also referred to as "closing ratio") of polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more from the viewpoint of film strength and insulation properties of the resulting organic film. do.

The upper limit of the imidization rate is not particularly limited, and may be 100% or less.

The imidization rate is measured by the same method as the closure rate of polyimide described above.

The polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R ¹¹¹ or R ¹¹⁷ , or the above-mentioned units containing two or more different types of R ¹³¹ or R ¹³² . It may contain a repeating unit represented by formula (PAI-3). In addition, polyamideimide may also contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the formula (PAI-1) or (PAI-2) described above.

Polyamideimide can be prepared, for example, by obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or by stopping the imidization reaction midway and partially imidizing it. It can be synthesized using a method of introducing an imide structure, or furthermore, a method of introducing a partial imide structure by blending a fully imidized polymer and its polyamideimide precursor.

The weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more.

Moreover, the number average molecular weight (Mn) of polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.

The molecular weight dispersion degree of polyamideimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the molecular weight dispersion of polyamideimide is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is still more preferable.

Moreover, when the resin composition contains multiple types of polyamideimide as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion degree of at least one type of polyamideimide are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion degree calculated from the plurality of types of polyamideimide as one resin are respectively within the above ranges.

[Method for producing polyimide precursor, etc.]

Polyimide precursors can be prepared, for example, by reacting tetracarboxylic dianhydride and diamine at low temperature, or by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid, and then esterifying it using a condensing agent or alkylating agent. method, obtain a diester using tetracarboxylic dianhydride and alcohol, then react with diamine in the presence of a condensing agent, obtain diester using tetracarboxylic dianhydride and alcohol, and then obtain the remaining dicarboxylic acid. It can be obtained by methods such as acid halogenation using a halogenating agent and reaction with diamine. Among the above production methods, a more preferred method is to obtain a diester using tetracarboxylic dianhydride and alcohol, then acid halogenate the remaining dicarboxylic acid using a halogenating agent and react it with diamine.

Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1,1-carbonyldioxy. -Di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc.

Examples of the alkylating agent include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. can be mentioned.

Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.

In methods for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one, and two or more types may be used.

Organic solvents can be appropriately determined depending on the raw materials, but include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, and dimethylacetamide. , dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. are exemplified.

In methods for producing polyimide precursors, etc., it is preferable to add a basic compound during reaction. The number of basic compounds may be one, and two or more types may be used.

The basic compound can be determined appropriately depending on the raw materials, but includes triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl- 4-aminopyridine and the like are exemplified.

-End sealant-

In a method for producing a polyimide precursor or the like, in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like. When sealing the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, terminal sealing agents include monoalcohol, phenol, thiol, thiophenol, monoamine, etc., and from the reactivity and film stability, monoalcohol , it is more preferable to use phenols or monoamines. Preferred monoalcohol compounds include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol. Secondary alcohols include secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. there is. Preferred phenol compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Also, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amino. Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2- Carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzene Sulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminocy Ofenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more types of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

Additionally, when sealing the amino group at the resin terminal, it is possible to seal it with a compound having a functional group capable of reacting with the amino group. Preferred sealants for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, and sulfonic carboxylic acid anhydrides, and more preferably carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Also, preferred compounds of carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-alcohol. Examples include damantane carbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

-Solid Precipitation-

In the production of polyimide precursors and the like, a step of precipitating solids may be included. Specifically, after filtering and separating the absorption by-products of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is added to a poor solvent such as water, lower aliphatic alcohol, or a mixture thereof. , a polyimide precursor, etc. can be obtained by precipitating the polymer component as a solid and drying it. In order to improve the degree of purification, operations such as re-dissolving the polyimide precursor, etc., re-precipitation, precipitation, and drying may be repeated. Additionally, a step of removing ionic impurities using an ion exchange resin may be included.

〔content〕

The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and 50% by mass, based on the total solid content of the resin composition. It is more preferable to have the above value. Moreover, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, based on the total solid content of the resin composition, and 97 It is more preferable that it is % by mass or less, and it is even more preferable that it is 95 % by mass or less.

The resin composition of the present invention may contain only one type of specific resin or may contain two or more types of specific resin. When two or more types are included, it is preferable that the total amount falls within the above range.

Moreover, it is preferable that the resin composition of this invention contains at least 2 types of resin.

Specifically, the resin composition of the present invention may contain a total of two or more types of a specific resin and other resins described later, and may contain two or more types of specific resins, but it is preferable to include two or more types of specific resins. .

When the resin composition of the present invention contains two or more types of specific resins, for example, as polyimide precursors, two or more types of polyimide precursors with different dianhydride-derived structures (R ¹¹⁵ in the above-mentioned formula (2)) are different. It is desirable to include.

<Other resins>

The resin composition of the present invention may contain the specific resin described above and another resin different from the specific resin (hereinafter also simply referred to as “other resin”).

Other resins include phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, Polyether resin, polyester resin, etc. can be mentioned.

For example, by further adding (meth)acrylic resin, a resin composition with excellent applicability is obtained, and a pattern (cured product) with excellent solvent resistance is obtained.

For example, instead of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable group with a weight average molecular weight of 20,000 or less and a high polymerizable group (for example, the molar amount of the polymerizable group contained in 1 g of the resin is 1) By adding a (meth)acrylic resin (at least x10 ^-3 mol/g) to the resin composition, the applicability of the resin composition, the solvent resistance of the pattern (cured product), etc. can be improved.

When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 1% by mass or more, based on the total solid content of the resin composition. It is preferable, it is more preferable that it is 2 mass % or more, it is still more preferable that it is 5 mass % or more, and it is still more preferable that it is 10 mass % or more.

Moreover, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less, based on the total solid content of the resin composition. , it is more preferable that it is 60 mass% or less, and it is even more preferable that it is 50 mass% or less.

Additionally, as a preferred aspect of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and 5% by mass or less, based on the total solid content of the resin composition. It is even more preferable, and it is even more preferable that it is 1% by mass or less. The lower limit of the above content is not particularly limited, and may be 0% by mass or more.

The resin composition of the present invention may contain only one type of other resin or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.

<Compound B>

The resin composition of the present invention contains compound B represented by formula (1-1).

[Formula 32]

X ¹ represents an n-valent ^linking group containing an aromatic ring structure, at least ^one of the bonding sites with the nitrogen atom in the formula for represents a group ^, R ¹ may ^{combine with} represents an integer of 1 or more, and m represents an integer of 1 or more.

〔X ¹ 〕

In Formula (1-1), X ¹ may contain only one aromatic ring structure or may contain two or more aromatic ring structures. The ^aromatic ring structure for It is more preferable to have a benzene ring structure. Examples of heteroatoms in the aromatic heterocyclic structure include oxygen atoms, sulfur atoms, and nitrogen atoms. In addition, the ^aromatic ring structure for

Moreover, when n is an integer of 2 or more, at least one ^of the bonding sites with the nitrogen atom in formula ( ^1-1 ) in One of the preferred aspects of the present invention is that all of the bonding sites with atoms have an aromatic ring structure.

In formula ( ^{1-1 )} _, It is a group represented by a combination of at least one type of group selected from the group consisting of, and is preferably a group containing at least one aromatic ring structure, and is preferably an aromatic ring structure or a hydrocarbon group, -O- and -C (= It is a group represented by a combination of at least one group selected from the group consisting of O)-, and is more preferably a group containing at least one aromatic ring structure, and is represented by the following formula (X-1) or formula (X-2) A group appearing as is more preferable. R ^N each independently represents a hydrogen atom or a hydrocarbon group, with a hydrogen atom, an alkyl group, or an aryl group being more preferable, a hydrogen atom or an alkyl group being more preferable, and a hydrogen atom being particularly preferable.

[Formula 33]

In formula (X-1), n is the same integer as n in formula (1-1), ^R ) represents the binding site with the nitrogen atom.

In the formula (X-2), n1 and n2 each independently represent an integer of 1 to 4, n1+n2 is the same integer as n in the formula (1-1), and ^R represents ^a single bond or a divalent linking group, b represents an integer from 0 to 5-n, c represents an integer from 0 to 5-n, and * represents nitrogen in formula (1-1). Indicates the bonding site with an atom.

In formula (X-1), n is preferably an integer of 1 to 4, and is more preferably 1 or 2. Additionally, the aspect in which n is 1 is also one of the preferred aspects of the present invention.

In formula (X-1), ^R , an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, a vinyl group, or a phenyl group is preferable, and a methyl group, a methoxy group, a vinyl group, or a phenyl group is more preferable.

In formula (X-1), a is preferably an integer of 0 to 2, and more preferably 0 or 1.

In formula (X-2), n1 is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

In the formula (X-2), n2 is preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.

In formula (X-2 ⁾ , ^R

In formula (X-2), L ¹ is preferably a single bond, a hydrocarbon group, -O-, -C(=O)-, -S-, or -S(=O) ₂ -, and is preferably a single bond or an alkyl group. Alternatively, a phenylene group is more preferable, a single bond or an alkyl group having 1 to 4 carbon atoms is more preferable, and a single bond or a methylene group is particularly preferable.

In formula (X-2), b is preferably an integer of 0 to 2, and is more preferably 0 or 1.

In formula (X-2), c is preferably an integer of 0 to 2, and more preferably 0 or 1.

Preferred aspects of X ¹ are shown below, but are not limited thereto. In the following specific examples, * represents a bonding site with a nitrogen atom in formula (1-1).

[Formula 34]

〔R ¹ 〕

In formula (1-1), R ¹ is each independently preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. ^In addition ^, R ¹ may combine ^with Examples of the ring structure formed include an indoline ring structure.

〔Y ¹ 〕

In formula (1-1), Y ¹ is a hydrocarbon group, or a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N - A group represented by a combination of at least one group selected from the group consisting of is preferable, and is selected from the group consisting of a hydrocarbon group or a hydrocarbon group, -O-, -C(=O)-, and -NR ^N -. A group represented by a combination of at least one type of group is more preferable. R ^N is the same as above.

The hydrocarbon group may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but Y ¹ preferably contains at least an aliphatic hydrocarbon group, and is more preferably a saturated aliphatic hydrocarbon group.

Moreover, from the viewpoint of chemical resistance, Y ¹ preferably also contains a urea bond, a urethane bond, or an amide bond. When Y ¹ includes a urethane bond or an amide bond, the direction of the urethane bond or amide bond is not particularly limited. For example, the structure of Y ¹ may include a group represented by the following formula (Y-1) as a structure containing a urethane bond.

[Formula 35]

In the formula ⁽ Y-1), It represents an organic group, R ¹ may be combined with X to form a ring structure, and represents a binding site with the structure of *.

In the formula (Y-1), the preferred aspect of X is the same as the preferred aspect of X ¹ when n is 1 in the formula (1-1).

In formula (Y-1), the preferred embodiment of R ¹ is the same as the preferred embodiment of R ¹ in formula (1-1).

Preferred aspects of Y ¹ are shown below, but are not limited thereto. In the following specific examples, # represents the bonding site with the oxygen atom in Formula (1-1), and * represents the bonding site with W ¹ .

[Formula 36]

〔W ¹ 〕

In formula (1-1), W ¹ is a group containing a polymerizable group.

Examples of the polymerizable group in W ¹ include a radical polymerizable group, an epoxy group, oxetanyl group, methylol group, and alkoxymethyl group, and a radical polymerizable group is preferable.

Examples of the radical polymerizable group include (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, styryl group, vinyl group, allyl group, maleimide group, etc.

As W ¹ , (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, vinylphenyloxy group, styryl group, vinyl group, vinyl ether group, allyl group, allyl ether group, and maleimide group are preferable, ( A meth)acryloxy group, (meth)acrylamide group, or maleimide group is more preferable.

[m, n]

In formula (1-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably an integer of 1 to 3, especially preferably 1 or 2, and 1 It is most desirable.

In formula (1-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably an integer of 1 to 3, especially preferably 1 or 2, and 1 It is most desirable.

[Number of atoms between the oxygen atom to which Y ¹ is bonded and W ¹ (chain length)]

In formula (1-1), the number of atoms (chain length) between the oxygen atom to which Y ¹ is bonded and W ¹ in compound B is not particularly limited, but is preferably 30 or less, and is 2 to 20. It is more preferable, and it is more preferable that it is 2 to 10.

When compound B contains 2 or more oxygen atoms bonded to Y ¹ , or when it contains 2 or more oxygen atoms bonded to Y ¹ , or when compound B contains 2 or more oxygen atoms bonded to Y ¹ and also contains 2 or more W ¹ In this case, the minimum number of atoms (linked chain length) between the oxygen atom to which Y ¹ is bonded and W ¹ may be within the above range.

In this specification, “the number of atoms (linked chain length) between the oxygen atom to which Y ¹ is bonded and W ¹ ” refers to the number of atoms in the atomic chain on the path connecting the two atoms or groups of atoms to be linked. This refers to connecting the connection object in the shortest possible manner (minimum number of atoms). For example, in the structure represented by the formula below, the number of atoms (linked chain length) between the oxygen atom to which Y ¹ is bonded and W ¹ (methacryloxy group) is 2.

[Formula 37]

〔Molecular Weight〕

The molecular weight of compound B is preferably 1,000 or less, preferably 100 to 900, and more preferably 200 to 800.

[Synthesis of Compound B]

Compound B can be synthesized, for example, by the method described in the Examples described later.

Additionally, the method for synthesizing Compound B is not particularly limited, and may be synthesized using other known methods.

Specific examples of compound B include SA-1 to SA-25 used in the examples, but are not limited thereto.

The content of compound B relative to the total mass of the resin composition of the present invention is preferably 1% by mass or more. As for the said content, it is more preferable that it is 2 mass % or more, and it is still more preferable that it is 3 mass % or more. Moreover, it is preferable that the said content is 20 mass % or less, and it is more preferable that it is 10 mass % or less.

Moreover, it is preferable that the content of compound B relative to the total solid content of the resin composition of the present invention is 1 to 40 mass%. The lower limit is more preferably 3% by mass or more, more preferably 5% by mass or more, and especially preferably 6% by mass or more. As for the upper limit, it is more preferable that it is 30 mass % or less, and it is still more preferable that it is 20 mass % or less.

Compound B may be used individually, or may be used in combination of two or more types. When using two or more types together, it is preferable that the total amount falls within the above range.

<Other polymerizable compounds>

The resin composition of the present invention preferably further contains a polymerizable compound different from the above-mentioned compound B (hereinafter also referred to as “another polymerizable compound”).

In particular, it is preferable that the radically polymerizable compound further contains a compound different from the compound B (a radical crosslinking agent described later).

Other polymerizable compounds are compounds having a polymerizable group and do not correspond to the above-mentioned compound B.

Other polymerizable compounds include radical crosslinking agents and other crosslinking agents, and those containing a radical crosslinking agent are preferred.

The content of the other polymerizable compound is preferably greater than 0% by mass and 20% by mass or less, based on the total mass of the composition. The lower limit of the content is preferably 0.1 mass% or more, more preferably 1.0 mass% or more, and even more preferably 1.5 mass% or more. The upper limit of the content is preferably 15% by mass or less, and more preferably 10% by mass or less.

The resin composition of the present invention may contain one type of other polymerizable compound or two or more types thereof. When two or more types are included, it is preferable that their total amount is within the above range.

In addition, when other polymerizable compounds are included, the content of the other polymerizable compounds relative to 100 parts by mass of compound B is preferably greater than 0 parts by mass*parts by mass or less, more preferably 5 parts by mass to 100 parts by mass, and 10 parts by mass. Parts by mass to 50 parts by mass are more preferable.

[Radical crosslinking agent]

The resin composition of the present invention preferably contains a radical crosslinking agent.

A radical crosslinking agent is a compound having a radical polymerizable group. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond, such as vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group.

Among these, as the group containing the ethylenically unsaturated bond, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferable, and from the viewpoint of reactivity, (meth)acryloyl group is more preferable.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.

As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds This is more preferable.

Moreover, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. .

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides, and preferably unsaturated carboxylic acids. These are esters of carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Additionally, addition reactants of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy, amino, or sulfanyl groups and mono- or poly-functional isocyanates or epoxies, or mono- or poly-functional carboxylic acids. Dehydration condensation reactants and the like are also suitably used. In addition, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups, monofunctional or polyfunctional alcohols, amines, and thiols, as well as halogeno groups, tosyloxy groups, etc. Substitution reactants of unsaturated carboxylic acid esters or amides having a dissociable substituent and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Also, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, the description in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and these contents are incorporated in this specification.

Additionally, the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol. Tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyl) Oxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then turning it into (meth)acrylate, Japan. Urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 51-037193. Polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490, and epoxy acrylic, which is a reaction product of epoxy resin and (meth)acrylic acid. Examples include polyfunctional acrylates and methacrylates, such as latex, and mixtures thereof. Additionally, the compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also suitable. Moreover, polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be mentioned.

Preferred radical crosslinking agents other than those described above include those described in JP2010-160418, JP2010-129825, JP4364216, etc., which have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups or cardo resin.

In addition, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, and Japanese Patent Publication No. 02-025493. Vinylphosphonic acid-based compounds described in No. 1, etc. can also be mentioned. Additionally, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Also, Journal of the Japan Adhesive Association, vol. 20, no. 7, pages 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, the contents of which are incorporated herein by reference.

In addition, ethylene oxide or propylene oxide is added to the polyfunctional alcohol described with specific examples as formula (1) and formula (2) in Japanese Patent Application Laid-Open No. 10-062986, followed by (meth)acrylate. The compound can also be used as a radical crosslinking agent.

In addition, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as a radical crosslinking agent, the contents of which are incorporated herein by reference.

As a radical crosslinking agent, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) product), A-TMMT (manufactured by Shinnakamura Chemical Industry Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaeryth Litol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shinnakamura Chemical Co., Ltd.)), and their (meth)acryloyl group is an ethylene glycol residue. Alternatively, a structure in which they are bonded through a propylene glycol residue is preferable. These oligomeric types can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains manufactured by Sartomer, and SR-209, a bifunctional methacrylate with four ethyleneoxy chains, manufactured by Sartomer. 231, 239, DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd., and urethane. Oligomer UAS-10, UAB-140 (manufactured by Nippon Seishi Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shinnakamura Chemical Co., Ltd.), DPHA- 40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (above, manufactured by Kyoeisha Kagaku Co., Ltd.), Blemmer PME400 (nippon Kayaku Co., Ltd.) Heoyu Co., Ltd.) and the like can be mentioned.

As radical cross-linking agents, those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765. Lethene acrylate luna, an ethylene oxide system described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Urethane compounds having a skeleton are also suitable. In addition, as a radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. You can also use it.

The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a radical cross-linking agent in which an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to provide an acid group is more preferable. do. Particularly preferably, in the radical crosslinking agent in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acidic group, the aliphatic polyhydroxy compound is a compound wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. am. Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the handleability during manufacture is excellent, and further, the developability is excellent. Additionally, it has good polymerizability. The acid value is measured based on the description of JIS K 0070:1992.

For the resin composition, it is preferable to use bifunctional methacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.

Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG (polyethylene glycol) 200. Diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate Rate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct of bisphenol A diacrylate, EO adduct of bisphenol A dimethacryl Rate, PO (propylene oxide) adduct of bisphenol A diacrylate, PO adduct of bisphenol A dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified die Acrylates, isocyanuric acid-modified dimethacrylates, other bifunctional acrylates with a urethane bond, and bifunctional methacrylates with a urethane bond can be used. These can be used in mixture of two or more types as needed.

In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, which means that the weight of the polyethylene glycol chain is about 200.

The resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a radical crosslinking agent from the viewpoint of suppressing bending by controlling the elastic modulus of the pattern (cured product). As monofunctional radical crosslinking agents, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and carbitol (meth)acrylate. Acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol (meth)acrylic acid derivatives such as mono(meth)acrylate and polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl Ether and the like are preferably used. As a monofunctional radical crosslinking agent, a compound having a boiling point of 100°C or higher under normal pressure is also preferred in order to suppress volatilization before exposure.

In addition, examples of the bifunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical crosslinking agent is contained, its content is preferably greater than 0% by mass and 60% by mass or less based on the total solid content of the resin composition of the present invention. As for the lower limit, 5 mass% or more is more preferable. As for the upper limit, it is more preferable that it is 50 mass % or less, and it is still more preferable that it is 30 mass % or less.

One type of radical crosslinking agent may be used individually, or two or more types may be mixed and used. When using two or more types together, it is preferable that the total amount falls within the above range.

[Other cross-linking agents]

It is also preferable that the resin composition of the present invention contains another crosslinking agent that is different from the radical crosslinking agent described above.

In the present invention, the other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above, and is shared with other compounds or reaction products thereof in the composition by photosensitization with the above-mentioned photoacid generator or photobase generator. It is preferable that the compound has a plurality of groups in the molecule that promote the reaction to form a bond, and the molecule contains a group that promotes the reaction that forms a covalent bond with other compounds in the composition or the reaction product thereof by the action of an acid or base. A compound having a plurality of compounds is preferred.

The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure process.

As another crosslinking agent, compounds having at least one group selected from the group consisting of an acyloxymethyl group, methylol group, and alkoxymethyl group are preferable, and at least one group selected from the group consisting of an acyloxymethyl group, methylol group, and alkoxymethyl group is preferably a nitrogen atom. A compound having a structure directly bonded to is more preferable.

As another crosslinking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol to convert the hydrogen atom of the amino group into an acyloxymethyl group or methyl. Examples include compounds having a structure substituted with an ol group or an alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Additionally, oligomers formed by self-condensation of the methylol groups of these compounds may be used.

As the above amino group-containing compound, the crosslinking agent using melamine is a melamine-based crosslinking agent, the crosslinking agent using glycoluril, urea or alkylene urea is a urea-based crosslinking agent, and the crosslinking agent using alkylene urea is an alkylene urea-based crosslinking agent and benzoguanamine. The cross-linking agent used is called a benzoguanamine-based cross-linking agent.

Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described later. It is more preferable to include at least one selected compound.

Examples of compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, on a nitrogen atom of the following urea structure, or on a triazine. Examples of structures include:

The alkoxymethyl group or acyloxymethyl group contained in the compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.

The total number of alkoxymethyl groups and acyloxymethyl groups in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.

The molecular weight of the compound is preferably 1500 or less, preferably 180 to 1200.

[Formula 38]

R ₁₀₀ represents an alkyl group or an acyl group.

R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group, and may be combined with each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group are directly substituted with an aromatic group include compounds having the following general formula.

[Formula 39]

_In the formula _, A group that is decomposed by action to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ is each independently a hydrogen atom or a carbon number) It represents an alkyl group of 1 to 4, and R ⁵ represents a group that is separated by the action of an acid.)).

R ₁₀₅ each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+ d is 5 or less, b+e is 4 or less, and c+f is 4 or less.

R 5 in a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group ^that is released by the action of an acid, and a group represented by -C(R ⁴ ) ₂ COOR ⁵ is, for example, -C ( R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ), etc.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. R ₃₆ and R ₃₇ may be combined with each other to form a ring.

As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.

The alkyl group may be either linear or branched.

As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.

The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.

The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.

The aralkyl group is intended to be an aryl group substituted by an alkyl group, and the preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the alkyl groups and aryl groups described above.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.

Moreover, these groups may further have known substituents within the range where the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The group that is decomposed by the action of an acid to generate an alkali-soluble group, or the group that is released by the action of an acid, is preferably a tertiary alkyl ester group, acetal group, cumyl ester group, or enol ester group. More preferably, it is a tertiary alkyl ester group or an acetal group.

Specific examples of compounds having an alkoxymethyl group include the following structures. Compounds having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group. Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.

[Formula 40]

[Formula 41]

The compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or one synthesized by a known method.

From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include, for example, monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, and monomethoxy. Methylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril , triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated Glycoluril-based crosslinking agents such as glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril. ;

Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea,

Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, diethoxymethylated ethylene urea, Ethylene urea-based crosslinking agents such as propoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea,

Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, Propylene urea-based crosslinking agents such as dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,

1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazoly Dinon, etc. may be mentioned.

Specific examples of benzoguanamine-based crosslinking agents include, for example, monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, and monomethoxymethylated benzoguanamine. Namine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, Tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, divu. Toxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc. can be mentioned.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring). Compounds are also suitably used.

Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, Hydroxymethylbenzoic acid Hydroxymethylphenyl, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl) Dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylbenzoic acid methoxymethylphenyl, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl) Biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(tri Fluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4 ,4'-diol, etc. can be mentioned.

As other crosslinking agents, commercial products may be used. Suitable commercial products include 46DMOC, 46DMOEP (above, manufactured by Asahi Yukizai Kogyo), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC- P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML- BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, manufactured by Honshu Kagaku High School), Nikalak ( Registered trademarks, same hereinafter) MX-290, Nikaloc MX-280, Nikaloc MX-270, Nikaloc MX-279, Nikaloc MW-100LM, Nikaloc MX-750LM (above, manufactured by Sanwa Chemical), etc. there is.

Additionally, the resin composition of the present invention preferably contains, as another crosslinking agent, at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound.

-Epoxy compound (compound having an epoxy group)-

The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a crosslinking reaction at 200°C or lower, and since the dehydration reaction resulting from crosslinking does not occur, film shrinkage is unlikely to occur. For this reason, containing an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and bending can be suppressed. A polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and it is preferable that the number of repeating units is 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; Bisphenol F-type epoxy resin; Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol Alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as diglycidyl ether and trimethylolpropane triglycidyl ether; Polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; Silicones containing epoxy groups such as polymethyl (glycidyloxypropyl) siloxane may be mentioned, but are not limited to these. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name above, manufactured by DIC Co., Ltd.), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (brand name, manufactured by Shin Nippon Rika Co., Ltd.), EP -4003S, EP-4000S, EP-4088S, EP-3950S (trade names above, manufactured by ADEKA Co., Ltd.), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150 , Epolyde (registered trademark) GT401, Epolyde (registered trademark) PB4700, Epolyde (registered trademark) PB3600 (trade names above, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC- 3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN- Examples include 502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (above product names, manufactured by Nippon Kayaku Co., Ltd.). . Additionally, the following compounds are also suitably used.

[Formula 42]

In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7 in terms of achieving both heat resistance and elongation improvement.

-Oxetane compound (compound having an oxetanyl group)-

Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy ]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. . As a specific example, the Aaron Oxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be suitably used, and these may be used alone or in a mixture of two or more types.

-Benzoxazine compound (compound having a benzoxazolyl group)-

Benzoxazine compounds are preferable because they prevent degassing during curing due to a crosslinking reaction resulting from a ring-opening addition reaction, and also reduce heat shrinkage and suppress the occurrence of warping.

Preferred examples of benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (above, brand name, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolac type dihydrobenz. Oxazine compounds may be mentioned. These may be used individually, or two or more types may be mixed.

The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition of the present invention. It is particularly preferable that it is 10% by mass. As for other crosslinking agents, only one type may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total is within the above range.

[Polymerization initiator]

The resin composition of the present invention preferably contains a polymerization initiator, and preferably contains a radical polymerization initiator. The radical polymerization initiator preferably includes a radical polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a radical photopolymerization initiator.

The radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a radical photopolymerization initiator that has photosensitivity to light from the ultraviolet region to the visible region is preferred. Additionally, it may be an activator that produces an active radical by producing some kind of effect with the photoexcited sensitizer.

The radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). desirable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure the concentration at a concentration of 0.01 g/L using an ethyl acetate solvent using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

As a radical photopolymerization initiator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide. , oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, and hydroxyacetophenone. Examples include α-hydroxyketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes. For these details, reference may be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference. Additionally, paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, MATERIAL STAGE 37 to 60 pages, vol. 19, no. 3, the peroxide-based photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864, Examples include the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-044030 and the peroxide-based initiator described in Japanese Patent Application Laid-Open No. 2019-167313, and these contents are also incorporated herein by reference.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, the content of which is incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

In one embodiment of the present invention, as a radical photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent Publication No. 4225898 can be used, the contents of which are described in this specification. It is used in

As α-hydroxyketone-based initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127. (Product name: all manufactured by BASF) can be used.

As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As an aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179, whose maximum absorption wavelength is matched to a light source with a wavelength of 365 nm or 405 nm, can also be used, the contents of which are incorporated herein by reference.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

As a radical photopolymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. Oxime compounds are particularly preferable because they have a wide exposure latitude (exposure margin) and also act as a photocuring accelerator.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, and J. C. S. Perkin II (1979, pp. 1653-1660), a compound described in J. C. S. Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), Japanese Patent Application Publication. Compounds described in No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent Application Publication No. 6065596, International Publication No. 2015/152153 Compounds described in, Compounds described in International Publication No. 2017/051680, Compounds described in Japanese Patent Application Publication No. 2017-198865, Compounds described in paragraph numbers 0025 to 0038 of International Publication No. 2017/164127, International Publication No. 2013 The compounds described in /167515, etc. can be mentioned, the contents of which are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3- (propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one , 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)(imino))butan-2-one, and 2-(ethoxycarbohydrate Nyloxy(imino))-1-phenylpropan-1-one, etc. can be mentioned. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based radical photopolymerization initiator) as a radical photopolymerization initiator. The oxime-based radical photopolymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[Formula 43]

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., the optical device described in Japanese Patent Application Publication No. 2012-014052). A radical polymerization initiator 2) is also suitably used. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Ackles NCI-730, NCI-831 and Deca Ackles NCI-930 (made by ADEKA Co., Ltd.) can also be used. Additionally, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Additionally, an oxime compound having the following structure can also be used.

[Formula 44]

As a radical photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and compounds described in Japanese Patent Application Publication No. 06636081, the contents of which are incorporated herein by reference.

As a radical photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring among carbazole rings becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, the content of which is incorporated herein by reference.

Additionally, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Laid-Open No. 2013- Compound (C-3) described in paragraph 0101 of No. 164471, etc., the content of which is incorporated herein by reference.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably used as a dimer. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and JP2014-137466. Examples include compounds described in paragraph numbers 0007 to 0025 of No. 4223071, the contents of which are incorporated herein by reference. In addition, examples of oxime compounds having a nitro group include Adeka Archles NCI-831 (manufactured by ADEKA Co., Ltd.).

As a radical photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As a radical photopolymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used. Such photopolymerization initiators include compounds described in International Publication No. 2019/088055, the content of which is incorporated herein by reference.

As a photopolymerization initiator, an oxime compound (hereinafter also referred to as oxime compound OX) having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into the aromatic ring can also be used. Examples of the electron withdrawing group possessed by the aromatic ring group Ar ^OX1 include acyl group, nitro group, trifluoromethyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and cyano group, and acyl group and A nitro group is preferable, an acyl group is more preferable because it is easy to form a film with excellent light resistance, and a benzoyl group is still more preferable. The benzoyl group may have a substituent. Substituents include halogen atom, cyano group, nitro group, hydroxy group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group, and more preferably an alkoxy group, an alkylsulfanyl group or an amino group. It is more desirable.

The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and is more preferably a compound represented by the formula (OX2).

[Formula 45]

In the formula, ^R Represents an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,

^R , represents an acyloxy group or an amino group,

^{R _}

However, at ^least one ^of R

In ^{the above formula , R}

Specific examples of oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, the contents of which are incorporated herein by reference.

The most preferable oxime compounds include oxime compounds having specific substituents shown in Japanese Patent Application Laid-Open No. 2007-269779, oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like. It is used herein.

From the viewpoint of exposure sensitivity, the radical photopolymerization initiator is trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, and metal. locene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complex and its salts, halomethyloxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

More preferable radical photopolymerization initiators include trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds. , a benzophenone compound, an acetophenone compound, and at least one selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound. A species compound is more preferable, and it is even more preferable to use a metallocene compound or an oxime compound.

In addition, the radical photopolymerization initiator is N,N'-tetraalkyl-4,4'-diamino such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), etc. Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholy Aromatic ketones such as no-propanone-1, quinones condensed with an aromatic ring such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyldimethylsiloxane. Benzyl derivatives such as methyl ketal can also be used. Moreover, a compound represented by the following formula (I) can also be used.

[Formula 46]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms. Alkyl group, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, alkyl group with 2 to 18 carbon atoms and 1 to 4 carbon atoms interrupted by one or more oxygen atoms. ^is a ^phenyl group or a ^biphenyl group substituted with at ^least one of the alkyl groups of , an alkoxy group or halogen atom having 1 to 12 carbon atoms.

[Formula 47]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

In addition, the radical photopolymerization initiator can also use the compound described in paragraphs 0048 to 0055 of International Publication No. 2015/125469, and this content is incorporated in this specification.

As a radical photopolymerization initiator, you may use a difunctional or trifunctional or more functional radical photopolymerization initiator. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity is obtained. In addition, when a compound with an asymmetric structure is used, crystallinity is lowered, solubility in solvents, etc. is improved, precipitation becomes difficult over time, and the temporal stability of the resin composition can be improved. Specific examples of di- or tri-functional or higher radical photopolymerization initiators include paragraphs of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. No. 0407-0412, dimer of the oxime compound described in paragraph number 0039-0055 of International Publication No. 2017/033680, compound (E) and compound (G) described in Japanese Patent Publication No. 2013-522445, Cmpd 1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph number 0007 of Japanese Patent Publication No. 2017-523465, and paragraph numbers 0020 to 0033 of Japanese Patent Publication No. 2017-167399. The photoinitiator described in , the photopolymerization initiator (A) described in paragraph numbers 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent Application Publication No. 6469669, etc., the contents of which are included. is used herein.

When a radical photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 0.5% by mass, based on the total solid content of the resin composition of the present invention. It is 15 mass%, and more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, and two or more types may be contained. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range.

Additionally, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further advanced in some cases by heating in an oven or a hot plate.

[Sensitizer]

The resin composition may contain a sensitizer. The sensitizer absorbs specific activating radiation and becomes electronically excited. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids, or bases.

Sensitizers that can be used include benzophenone, Michler's ketone, coumarin, pyrazolazo, anilinoazo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, and pyrazine. Compounds such as zolotriazoleazo, pyridonezo, cyanine, phenocyazine, pyrrolopyrazoleazomethane, xanthene, phthalocyanine, benzopyran, and indigo compounds can be used.

As a sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis( 4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2 -(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1 ,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl -7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin ( 7-(diethylamino)coumarin-3-carboxylic acid ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholy Nobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p- Dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2- (p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

Additionally, other sensitizing dyes may be used.

For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and this content is incorporated herein by reference.

When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10% by mass, based on the total solid content of the resin composition. It is more preferable to be Sensitizers may be used individually, or two or more types may be used in combination.

[Chain transfer system]

The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Dictionary of Polymers, 3rd edition (Polymer Society edition, 2005), pages 683-684. As chain transfer agents, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH, and GeH in the molecule, and those used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization. Dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having a thiocarbonylthio group are used. These can generate radicals by donating hydrogen to low-activity radicals, or by deprotonating them after being oxidized. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. ~5 parts by mass is more preferable. There may be only one type of chain transfer agent, or two or more types may be used. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.

<Base generator>

The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base through physical or chemical action. Preferred base generators for the resin composition of the present invention include thermobase generators and photobase generators.

In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermobase generator, the cyclization reaction of the precursor can be promoted, for example, by heating, and the cured product has good mechanical properties and chemical resistance, for example, for the redistribution layer contained in a semiconductor package. Performance as an interlayer insulating film improves.

The base generator may be an ionic base generator or a non-ionic base generator. Examples of bases generated from base generators include secondary amines and tertiary amines.

There is no particular limitation on the base generator according to the present invention, and known base generators can be used. Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, and nitrobenzylcarbamate compounds. , sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthal Imide derivative compounds, acyloxyimino compounds, etc. can be used.

Specific examples of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).

[Formula 48]

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ each independently represent an organic group, a halogen atom or a hydrogen atom without a tertiary amine structure. However, Rb ¹ and Rb ² never become hydrogen atoms at the same time. In addition, Rb ¹ , Rb ² and Rb ³ do not all have a carboxyl group. In addition, in this specification, the tertiary amine structure refers to a structure in which all three bonding hands of a trivalent nitrogen atom are covalently bonded to hydrocarbon-based carbon atoms. Therefore, the case where the bonded carbon atom is a carbon atom forming a carbonyl group, that is, the case where it forms an amide group together with a nitrogen atom, is not limited to this.

In formulas (B1) and (B2), it is preferable that at least one of Rb ¹ , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are fused together is preferred. The monocycle is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is more preferable. As for a single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and more preferably 3 to 12), or an alkenyl group (preferably having 2 to 24 carbon atoms). , 2 to 18 are more preferable, 3 to 12 are more preferable), an aryl group (carbon numbers are preferably 6 to 22, more preferably 6 to 18, and 6 to 10 are more preferable), or an arylalkyl group ( It is preferable that the number of carbon atoms is 7 to 25, more preferably 7 to 19, and more preferably 7 to 12. These groups may have substituents within the range that exhibits the effects of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly preferably a straight-chain, branched, or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent. , a cycloalkyl group which may have a substituent (carbon number is preferably 3 to 24, more preferably 3 to 18, and 3 to 12 are more preferable), and a cyclohexyl group which may have a substituent is more preferable. do.

Rb ³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferable), alkenyl group (carbon atoms are preferably 2 to 24, more preferably 2 to 12, and 2 to 6 are more preferable), arylalkyl group (carbon atoms are preferably 7 to 23, and 7 to 19 is more preferable, 7 to 12 are more preferable), arylalkenyl group (carbon number is 8 to 24, more preferably 8 to 20, more preferably 8 to 16), alkoxyl group (carbon number is 1 to 16) 24 is preferable, 2 to 18 are more preferable, and 3 to 12 are more preferable), an aryloxy group (carbon number is preferably 6 to 22, more preferably 6 to 18, and 6 to 12 are more preferable) , or an arylalkyloxy group (carbon number 7 to 23 is preferable, 7 to 19 are more preferable, and 7 to 12 are more preferable). Among them, a cycloalkyl group (carbon number 3 to 24 is preferable, 3 to 18 are more preferable, and 3 to 12 are still more preferable), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent within the range that produces the effect of the present invention.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

[Formula 49]

In the formula, Rb ¹¹ and Rb ¹² and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.

Rb ¹³ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18, more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and 3 ~12 is more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, more preferably 6 to 12), arylalkyl group (carbon number is preferably 7 to 23, 7 to 19) is more preferable, and 7 to 12 is more preferable), and may have a substituent within the range showing the effect of the present invention. Among them, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and more preferably 1 to 3), or an alkenyl group (preferably having 2 to 12 carbon atoms) , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), arylalkyl group ( 7 to 23 carbon atoms are preferable, 7 to 19 carbon atoms are more preferable, and 7 to 11 carbon atoms are more preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 are more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, and 6 to 12 are more preferable), arylalkyl group (carbon number is preferably 7 to 23, and 7 to 19 is more preferable, 7 to 12 are more preferable), and an aryl group is preferable.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

[Formula 50]

Rb ¹¹ and Rb ¹² have the same meaning as Rb ¹¹ and Rb ¹² in formula (B1-1).

Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, and more preferably 1 to 3 carbon atoms), or an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms) It is more preferable, 2 to 3 is more preferable), aryl group (carbon number is 6 to 22 is preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (carbon number is 7 to 23) preferred, 7 to 19 are more preferred, and 7 to 11 are more preferred), and a hydrogen atom or a methyl group is preferred.

Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12, more preferably 3 to 8), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10, 3 ~8 is more preferable), aryl group (carbon number is preferably 6 to 22, more preferably 6 to 18, more preferably 6 to 12), arylalkyl group (carbon number is preferably 7 to 23, 7 to 19) is more preferable, and 7 to 12 are more preferable), and among them, an aryl group is preferable.

[Formula 51]

In formula (B3), L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group with 3 or more atoms on the path of the linking chain. indicates. Additionally, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, the term “connected chain” refers to the shortest (minimum number of atoms) connection of the atomic chains on the path connecting two atoms or groups of atoms. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain is ( In other words, the number of atoms constituting the linking chain (hereinafter also referred to as “linking chain length” or “linking chain length”) is 4.

[Formula 52]

The number of carbon atoms in L in the formula (B3) (including carbon atoms other than those in the linked chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and especially preferably 8 or less. As for the lower limit, it is more preferable that it is 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the chain length of L is preferably 12 or less, more preferably 8 or less, more preferably 6 or less, and especially preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds of the base generator include, for example, the compounds described in paragraph numbers 0102 to 0168 of International Publication No. 2020/066416, and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002. .

Moreover, it is preferable that the base generator also contains a compound represented by the following formula (N1).

[Formula 53]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, and is preferably a divalent organic group. The chain length of the linking group is preferably 1 or more, and more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length is the number of atoms present in the atomic arrangement that is the shortest distance between two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), and are hydrocarbon groups. (carbon number 1 to 24 is preferable, 1 to 12 is more preferable, and 1 to 10 are more preferable), and specifically, it is an aliphatic hydrocarbon group (carbon number 1 to 24 is preferable, and 1 to 12 is more preferable, and 1 to 10 are more preferable) or an aromatic hydrocarbon group (carbon number is preferably 6 to 22, more preferably 6 to 18, and 6 to 10 are more preferable), and aliphatic hydrocarbon group. Hydrogen groups are preferred. As R ^N1 and R ^N2 , it is preferable to use an aliphatic hydrocarbon group because the base generated has high basicity. Additionally, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an aspect in which an aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a linear or branched chain alkyl group, a cyclic alkyl group, a group related to a combination of a chain alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Straight-chain or branched alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, Examples include isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, and isohexyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.

The group related to the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and still more preferably 4 to 12 carbon atoms. Examples of groups that are a combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group.

The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain-shaped or cyclic, and may be straight-chain or branched.

Among them, from the viewpoint of increasing the boiling point of the decomposition product base described later, R ^N1 and R ^N2 are preferably an alkyl group having 5 to 12 carbon atoms. However, in formulations that place emphasis on adhesion when laminated with a metal (for example, copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.

R ^N1 and R ^N2 may be connected to each other to form a cyclic structure. When forming a cyclic structure, it may have an oxygen atom or the like in the chain. In addition, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic ring or a condensed ring, but a monocyclic structure is preferable. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, and an imidazolidine ring. , pyrazolidine ring, piperidine ring, piperazine ring, morpholine ring, etc. are mentioned, and pyrroline ring, pyrrolidine ring, piperidine ring, piperazine ring, and morpholine ring are preferably mentioned.

R ^C1 represents a hydrogen atom or a protecting group, and a hydrogen atom is preferable.

As the protecting group, a protecting group that is decomposed by the action of an acid or base is preferable, and a protective group that is decomposed by an acid is preferable.

Specific examples of the protecting group include a chain-shaped or cyclic alkyl group, or a chain-shaped or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl group, ethyl group, isopropyl group, tert-butyl group, and cyclohexyl group. Examples of the chain-shaped alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and more specifically, a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of the cyclic alkyl group having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, and tetrahydropyranyl (THP) group.

The divalent linking group constituting L is not particularly defined, but a hydrocarbon group is preferable and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent or may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or an oxygen atom in the chain. A group that is a combination of a divalent aliphatic hydrocarbon group that may have a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain is more preferable. It is preferable that these groups do not have an oxygen atom.

The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms. The group (e.g., arylene alkyl group) that is a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms. desirable.

The linking group L specifically includes a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, and a linear or branched chain alkenyl group. A lene group, a cyclic alkenylene group, an arylene group, and an arylene alkylene group are preferable.

The linear or branched alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.

The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms.

The group related to the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and still more preferably 4 to 6 carbon atoms.

The alkylene group having an oxygen atom in the chain may be chain-shaped or cyclic, and may be straight-chain or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.

The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms. As for the linear or branched alkenylene group, the number of C=C bonds is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.

The cyclic alkenylene group preferably has 3 to 12 carbon atoms, and more preferably has 3 to 6 carbon atoms. As for the cyclic alkenylene group, the number of C=C bonds is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.

The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.

The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and still more preferably 7 to 11 carbon atoms.

Among them, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain-shaped alkenylene group, an arylene group, and an arylene alkylene group are preferable, and 1,2-ethylene group and propanediyl group (especially 1 , 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylenemethylene Groups (particularly 1,2-phenylenemethylene group) and ethyleneoxyethylene groups (particularly 1,2-ethyleneoxy-1,2-ethylene group) are more preferable.

Examples of the base generator include the following, but the present invention is not to be construed as being limited thereto.

[Formula 54]

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and still more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds of the ion-type base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018/038002.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

[Formula 55]

Specific examples of iminium salts include the following compounds, but the present invention is not limited to these.

[Formula 56]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, and may be 4 parts by mass or less.

One type or two or more types of base generators can be used. When using two or more types, it is preferable that the total amount is within the above range.

<Solvent>

It is preferable that the resin composition of the present invention contains a solvent.

As the solvent, any known solvent can be used arbitrarily. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionic acid methyl, 3-alkyloxy Ethyl propionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g. For example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. 2-methoxy-2-methylpropionate) methyl, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, Suitable examples include ethyl heptanoate, dimethyl malonate, and diethyl malonate.

As ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol. Lycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl Cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene Suitable examples include glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone. You can.

Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

Suitable examples of sulfoxides include dimethyl sulfoxide.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Formamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetyl Suitable examples include morpholine and the like.

Suitable examples of ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2- Propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Colmonomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono Phenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

It is also preferable that two or more types of solvents are mixed from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptane. cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and One type of solvent selected from propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent consisting of two or more types is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the viewpoint of applicability, the solvent content is preferably such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, and 10 It is more preferable to set it as ~70 mass%, and it is still more preferable to set it to 20-70 mass%. The solvent content may be adjusted according to the desired thickness of the coating film and the application method.

The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more types of solvents, it is preferable that the total is within the above range.

<Metal adhesion improver>

The resin composition of the present invention preferably contains a metal adhesion improving agent for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β- Keto ester compounds, amino compounds, etc. can be mentioned.

[Silane coupling agent]

Silane coupling agents include, for example, the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, and the compounds described in paragraph 0063 of International Publication No. 2011/080992. Compounds described in to 0071, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, compounds described in paragraphs 0055 of International Publication No. 2014/097594 Compounds include compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. Additionally, it is also preferable to use two or more different types of silane coupling agents as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Moreover, it is also preferable to use the following compounds as the silane coupling agent. In the formulas below, Me represents a methyl group and Et represents an ethyl group.

[Formula 57]

Other silane coupling agents include, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyl. Dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Silane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl -3-Aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mer Captopropyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride can be mentioned. These can be used individually or in combination of two or more types.

[Aluminum-based adhesive aid]

Examples of the aluminum-based adhesion aid include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), and ethyl acetoacetate aluminum diisopropylate.

In addition, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used. is used herein.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, with respect to 100 parts by mass of the specific resin. By setting it above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The number of metal adhesion improving agents may be one, or two or more types may be used. When using two or more types, it is preferable that the total is within the above range.

<Migration inhibitor>

It is preferable that the resin composition of the present invention further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress metal ions derived from the metal layer (metal wiring) from moving into the film.

There are no particular restrictions on the migration inhibitor, but heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine) Compounds having a ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and sulfanyl group A compound having a, hindered phenol-based compound, salicylic acid derivative-based compound, and hydrazide derivative-based compound can be mentioned. In particular, triazole-based compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; Tetrazole-based compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion trap agent that captures anions such as halogen ions can be used.

Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, compounds described in paragraph 0052 of JP2011-059656, The compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, the compounds described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used, the contents of which are incorporated herein by reference.

Specific examples of migration inhibitors include the following compounds.

[Formula 58]

When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, based on the total solid content of the resin composition of the present invention. It is more preferable that it is 0.1-1.0 mass %.

The number of migration inhibitors may be one, or two or more types may be used. When there are two or more migration inhibitors, it is preferable that the total is within the above range.

<Polymerization inhibitor>

The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl free radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, and metal compounds.

Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, and p-tert-butylcate. Col, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6 -tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine , ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8 -Hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitro So-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-t-butyl-3- Hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6 -Tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhyde Razyl, dibutyl dithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are suitable. It is used. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Laid-Open No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, the contents of which are incorporated herein by reference.

When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and more preferably 0.02 to 15% by mass, based on the total solid content of the resin composition of the present invention. And, it is more preferable that it is 0.05 to 10 mass%.

The number of polymerization inhibitors may be one, or two or more types may be used. When there are two or more polymerization inhibitors, it is preferable that the total is within the above range.

<Other additives>

The resin composition of the present invention contains various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, and antioxidants, as necessary, to the extent that the effects of the present invention are obtained. , anti-agglomeration agents, phenol-based compounds, other polymer compounds, plasticizers, and other aids (e.g., anti-foaming agents, flame retardants, etc.) can be blended. By appropriately containing these components, properties such as membrane physical properties can be adjusted. These components are, for example, described in Japanese Patent Application Publication No. 2012-003225, paragraph number 0183 onward (paragraph number 0237 of corresponding U.S. Patent Application Publication No. 2013/0034812), and paragraph numbers of Japanese Patent Application Publication No. 2008-250074. Reference may be made to descriptions such as 0101 to 0104, 0107 to 0109, etc., and these contents are incorporated herein by reference. When blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔Surfactants〕

As the surfactant, various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By containing a surfactant in the resin composition of the present invention, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of application thickness and liquid saving can be further improved. That is, in the case of forming a film using a coating liquid containing a composition containing a surfactant, the interfacial tension between the surface to be applied and the coating liquid is lowered, the wettability to the surface to be coated is improved, and the applicability to the surface to be coated is improved. It improves. For this reason, it is possible to more suitably form a film of uniform thickness with little thickness unevenness.

Examples of fluorine-based surfactants include Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, and F143. F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novek FC4430, FC4432 (manufactured by 3M Japan Co., Ltd.) Pron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass) Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 2011-132503 may be used, the contents of which are incorporated herein by reference. . A block polymer can also be used as a fluorine-based surfactant, and specific examples include compounds described in Japanese Patent Application Laid-Open No. 2011-89090, the contents of which are incorporated herein by reference.

The fluorine-based surfactant is a (meth) compound having a repeating unit derived from a (meth)acrylate compound having a fluorine atom and at least 2 (preferably at least 5) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups). ) Fluorine-containing polymer compounds containing repeating units derived from acrylate compounds can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Formula 59]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.

As the fluorinated surfactant, a fluorinated polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorinated surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, the contents of which are incorporated herein by reference. Additionally, commercially available products include, for example, Megapak RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorine-based surfactant is suitably 3 to 40 mass%, more preferably 5 to 30 mass%, and particularly preferably 7 to 25 mass%. A fluorine-based surfactant with a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

Silicone-based surfactants include, for example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Silicone SH8400) (manufactured by), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (above, manufactured by Big Chemi Co., Ltd.), etc.

Hydrocarbon-based surfactants include, for example, Pionin A-76, Newcargen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T (above, manufactured by Takemoto Yushi Corporation), etc.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl. Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. , sorbitan fatty acid ester, etc. are exemplified. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), and Solsperse 20000 (manufactured by BASF). (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Junyaku Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Yushi Takemoto (manufactured by Nisshin Chemical Co., Ltd.), Allfin E1010, and Surfynol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

As a cationic surfactant, specifically, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflo No. 75, no. 77, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

Specific examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Corporation), Sandet BL (manufactured by Sanyo Kasei Corporation), and the like.

Only one type of surfactant may be used, or two or more types may be used in combination.

The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.

[Advanced fatty acid derivatives]

In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention and distributed on the surface of the resin composition of the present invention during the drying process after application. .

Moreover, as a higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used, the content of which is incorporated herein by reference.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition of the present invention. There may be only one type of high-grade fatty acid derivative, or two or more types may be used. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.

[Thermal polymerization initiator]

The resin composition of this invention may contain a thermal polymerization initiator, and may especially contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals using heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be promoted, and thus the solvent resistance can be further improved. In addition, the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554, the contents of which are incorporated herein by reference.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition of the present invention. It is mass%. The thermal polymerization initiator may contain only one type, or may contain two or more types. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is within the above range.

[Inorganic particles]

The resin composition of the present invention may contain inorganic particles. The inorganic particles may specifically include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

As an average particle diameter of the said inorganic particle, 0.01-2.0 micrometers are preferable, 0.02-1.5 micrometers are more preferable, 0.03-1.0 micrometers are more preferable, and 0.04-0.5 micrometers are especially preferable.

The average particle diameter of the inorganic particles is the primary particle diameter and is also the volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).

In cases where the above measurement is difficult, measurement can also be performed by centrifugal precipitation light transmission, X-ray transmission, or laser diffraction/scattering.

[UV absorbent]

The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, etc. UV absorbers can be used.

Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihyde. Roxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. are mentioned. Additionally, examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole , 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole Azole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc. are mentioned.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Additionally, examples of triazine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di Methylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4 -Dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. mono(hydroxyphenyl)triazine compounds; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3 -methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6 Bis(hydroxyphenyl)triazine compounds such as -(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2- Hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]- and tris(hydroxyphenyl)triazine compounds such as 1,3,5-triazine.

In the present invention, the above-described various ultraviolet absorbers may be used individually or in combination of two or more types.

The composition of the present invention may or may not contain a ultraviolet absorber, but when included, the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.01 mass% or more and 0.1 mass% or less.

[Organic titanium compound]

The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer with excellent chemical resistance can be formed even when cured at low temperature.

Organic titanium compounds that can be used include those in which an organic group is bonded to a titanium atom through a covalent bond or ionic bond.

Specific examples of organic titanium compounds are shown in I) to VII) below:

I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentane dionate), and titanium diisopropoxide bis(2,4-phene). Tein dionate), titanium diisopropoxide bis(tetramethylheptane dionate), titanium diisopropoxide bis(ethylacetoacetate), etc.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium Tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethyl phenoxide, titanium tetra(n-nonyl oxide), titanium tetra(n-propoxide), titanium tetrastearyl oxide, titanium tetrakis[bis{2 , 2-(allyloxymethyl) butoxide}], etc.

III) Titanocene compounds: e.g. pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) ) titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc.

IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compounds: For example, titanium oxide bis(pentane dionate), titanium oxide bis(tetramethylheptane dionate), phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate.

VII) Titanate coupling agent: For example, isopropyl tridodecylbenzenesulfonyl titanate.

Among them, the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, which shows better chemical resistance. It is desirable in In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro). Ro-3-(1H-pyrrol-1-yl)phenyl)titanium is preferred.

When blending an organic titanium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the obtained cured pattern, while when the amount is 10 parts by mass or less, the storage stability of the composition is more excellent.

[Antioxidant]

The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the film after curing and the adhesion to the metal material can be improved. Examples of antioxidants include phenol compounds, phosphorous acid ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. Compounds having a substituent at the site (orthosite) adjacent to the phenolic hydroxy group are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Also, the antioxidant is preferably a compound having a phenol group and a phosphorous acid ester group in the same molecule. Additionally, phosphorus-based antioxidants can also be suitably used as antioxidants. As a phosphorus-based antioxidant, tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6- yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl) Oxy]ethyl]amine, ethylbisphosphorous acid (2,4-di-tert-butyl-6-methylphenyl), etc. Commercially available antioxidants include, for example, Adeka Stab AO-20, Adeka Stab AO-30, Adeka Stab AO-40, Adeka Stab AO-50, Adeka Stab AO-50F, Adeka Stab AO-60, Adeka Stab AO-60G, Adeka Stab AO-80, Adeka Stab AO-330 (above, manufactured by ADEKA Co., Ltd.), etc. In addition, the antioxidant can also be a compound described in paragraph numbers 0023 to 0048 of Japanese Patent Publication No. 6268967, the contents of which are incorporated herein by reference. Additionally, the composition of the present invention may contain a latent antioxidant if necessary. Potential antioxidants are compounds where the portion that functions as an antioxidant is protected by a protecting group, and when heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst, the protecting group is removed and functions as an antioxidant. Compounds may be mentioned. Potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include Adeka Ackles GPA-5001 (manufactured by ADEKA Co., Ltd.).

Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by formula (3).

[Formula 60]

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group with 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R ⁶ represents an alkylene group with 2 or more carbon atoms (preferably 2 to 10 carbon atoms). . R ⁷ represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, or a nitrogen atom. k represents an integer from 1 to 4.

The compound represented by formula (3) suppresses oxidative degradation of the aliphatic group or phenolic hydroxyl group contained in the resin. Additionally, metal oxidation can be suppressed due to the rust prevention effect on metal materials.

Since it can act on resin and metal materials simultaneously, k is more preferably an integer of 2 to 4. As R7, alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl group, arylether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, -O-, - Examples include NH-, -NHNH-, and combinations thereof, and may have additional substituents. Among these, those having an alkyl ether group and -NH- are preferable in terms of solubility in a developer and adhesion to metals, and -NH- is more preferable in terms of metal adhesion due to interaction with the resin and metal complex formation. .

Examples of the compound represented by General Formula (3) include the following, but are not limited to the following structure.

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By setting the addition amount to 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials is easy to obtain even in a high temperature and high humidity environment, and by setting it to 10 parts by mass or less, for example, due to interaction with the photosensitive agent, the resin The sensitivity of the composition is improved. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[Anti-agglomeration agent]

The resin composition of this embodiment may contain an anti-aggregation agent as needed. Examples of the anti-agglomeration agent include sodium polyacrylate.

In the present invention, one type of anti-aggregation agent may be used individually, or two or more types may be used in combination.

The composition of the present invention may or may not contain an anti-agglomeration agent, but when included, the content of the anti-aggregation agent is preferably 0.01% by mass or more and 10% by mass or less with respect to the total solid mass of the composition of the present invention, It is more preferable that it is 0.02 mass % or more and 5 mass % or less.

[Phenol-based compounds]

The resin composition of this embodiment may contain a phenol-based compound as needed. As phenolic compounds, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS -2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (above, brand name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F (above, brand name, manufactured by Asahi Yukizai Kogyo Co., Ltd.), etc. can be mentioned.

In the present invention, phenol-based compounds may be used individually or in combination of two or more types.

The composition of the present invention may or may not contain a phenol-based compound, but when included, the content of the phenol-based compound is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention. And, it is more preferable that it is 0.02 mass% or more and 20 mass% or less.

[Other polymer compounds]

Other high molecular compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups are introduced.

In the present invention, other polymer compounds may be used individually or in combination of two or more types.

The composition of the present invention may or may not contain other polymer compounds, but when included, the content of the other polymer compound is preferably 0.01% by mass or more and 30% by mass or less with respect to the total solid mass of the composition of the present invention. And, it is more preferable that it is 0.02 mass% or more and 20 mass% or less.

<Characteristics of resin composition>

The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000mm ² /s to 12,000mm ² /s is preferable, 2,000mm ² /s to 10,000mm ² /s is more preferable, and 2,500mm ² /s to 8,000mm ² /s is preferable. It is more desirable. Within the above range, it becomes easy to obtain a highly uniform coating film. If it is 1,000 mm ² /s or more, it is easy to apply the film to a thickness required as, for example, an insulating film for rewiring, and if it is 12,000 mm ² /s or less, a film with an excellent coated surface appearance can be obtained.

<Restrictions on substances contained in the resin composition>

The water content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and still more preferably less than 1.0 mass%. If it is less than 2.0%, the storage stability of the resin composition improves.

Methods for maintaining the moisture content include adjusting the humidity in storage conditions and reducing the porosity of the storage container during storage.

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, it is preferable that the total of these metals is within the above range.

Additionally, as a method of reducing metal impurities unintentionally contained in the resin composition of the present invention, raw materials with a low metal content are selected as the raw materials constituting the resin composition of the present invention, or raw materials constituting the resin composition of the present invention are selected. Methods such as performing filter filtration or lining the inside of the device with polytetrafluoroethylene or the like to perform distillation under conditions that suppress contamination as much as possible are examples.

Considering the use of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. It is more desirable. Among them, the amount of the halogen ion present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Halogen atoms include chlorine atoms and bromine atoms. It is preferable that the sum of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, respectively, is within the above range.

As a method for controlling the content of halogen atoms, ion exchange treatment or the like is preferably used.

As a container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing the incorporation of impurities into the raw materials or the resin composition of the present invention, a multi-layer bottle whose inner wall is composed of 6 types of 6-layer resins, or a bottle with 6 types of resins in a 7-layer structure. It is also desirable to use . Examples of such containers include those described in Japanese Patent Application Publication No. 2015-123351.

<Cured product of resin composition>

By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.

The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.

The curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and more preferably in the range of 170°C to 350°C. It is particularly desirable to be within the range. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as film-like, rod-like, spherical, or pellet-like. In the present invention, this cured product is preferably in the form of a film. In addition, through pattern processing of the resin composition, it can be tailored to the application, such as forming a protective film on the wall, forming via holes for conduction, adjusting impedance, capacitance or internal stress, and providing a heat dissipation function. The shape of this cured product can also be selected. The film thickness of this cured product (film consisting of the cured product) is preferably 0.5 μm or more and 150 μm or less.

The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change before and after curing of the resin composition, and can be calculated from the following formula.

Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

<Characteristics of the cured product of the resin composition>

The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, a cured product with excellent mechanical properties may be obtained.

The breaking elongation of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more.

The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of resin composition>

The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be performed by a conventionally known method.

Mixing can be done using a stirring blade, mixing using a ball mill, mixing by rotating the tank itself, etc.

The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

Additionally, for the purpose of removing foreign substances such as dust and fine particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter may be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable to use HDPE (high-density polyethylene). The filter may be one that has been previously washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected and used in series or parallel. When using multiple types of filters, filters with different pore diameters or materials may be used in combination. As a connection mode, for example, an HDPE filter with a pore diameter of 1 μm as the first stage is connected in series, and an HDPE filter with a pore diameter of 0.2 μm as the second stage is connected in series. Additionally, various materials may be filtered multiple times. When filtering multiple times, circular filtration may be used. Additionally, filtration may be performed under pressure. When performing filtration by pressurizing, the pressurizing pressure may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.05 MPa or more. 0.5 MPa or less is more preferable.

In addition to filtration using a filter, treatment to remove impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and a further step of degassing may be performed.

(Method for producing cured product)

The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

In addition, the method for producing a cured product of the present invention includes the film forming process, an exposure process of selectively exposing the film formed by the film forming process, and developing the film exposed by the exposure process using a developer to form a pattern. It is more preferable to include a process.

The method for producing a cured product of the present invention includes the film forming process, the exposure process, the developing process, and a heating process for heating the pattern obtained by the developing process, and a post-development exposure process for exposing the pattern obtained by the developing process. It is particularly preferable to include at least one party.

Additionally, the manufacturing method of the present invention preferably includes the film forming step and the step of heating the film.

Hereinafter, details of each process will be described.

<Film formation process>

The resin composition of the present invention can be used in a film forming process in which a film is formed by applying it on a substrate.

The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film.

〔write〕

The type of substrate can be appropriately determined depending on the application, but includes semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, Ni , metal substrates such as Cu, Cr, and Fe (for example, any of the substrates formed of metal and the metal layer may be formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), Examples include TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDP), but are not particularly limited. In the present invention, a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate, and a mold substrate are more preferable.

Additionally, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.

Additionally, the shape of the base material is not particularly limited and may be circular or rectangular.

As for the size of the base material, if it is circular, the diameter is, for example, 100 to 450 mm, and preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, and preferably 200 to 700 mm.

Additionally, as the base material, for example, a plate-shaped base material (substrate), preferably a panel shape, is used.

In addition, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured material) or a metal layer to form a film, the resin layer or the metal layer serves as a base material.

As a means of applying the resin composition of the present invention to a substrate, application is preferable.

As applied means, specifically, dip coat method, air knife coat method, curtain coat method, wire bar coat method, gravure coat method, extrusion coat method, spray coat method, spin coat method, slit coat method, and inkjet method. Laws, etc. are examples. From the viewpoint of film thickness uniformity, spin coating method, slit coating method, spray coating method, or inkjet method is more preferable, and from the viewpoint of film thickness uniformity and productivity, spin coating method and slit coating method are preferable. do. By adjusting the solid content concentration or application conditions of the resin composition according to the method, a film of desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet methods are preferable, and for rectangular substrates, slit coating, spray coating, and inkjet methods are preferable. etc. are preferable. In the case of the spin coat method, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.

In addition, a method of transferring the coating film previously formed by applying it on a temporary support by the above-described application method to a substrate can also be applied.

Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can be suitably used in the present invention.

Additionally, a step of removing excess film from the end portion of the substrate may be performed. Examples of such processes include edge bead rinse (EBR), back rinse, etc.

Additionally, a prewet process may be employed in which various solvents are applied to the substrate before applying the resin composition to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>

After the film formation process (layer formation process), the film may be subjected to a process for drying the formed film (layer) to remove the solvent (drying process).

That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step.

Additionally, the drying process is preferably performed after the film forming process and before the exposure process.

The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Additionally, drying may be performed under reduced pressure. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure process>

The film may be subjected to an exposure process that selectively exposes the film.

That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step.

Selectively exposing means exposing a part of the film. Additionally, by selective exposure, an exposed area (exposed area) and an unexposed area (non-exposed area) are formed in the film.

The exposure amount is not particularly determined as long as it can cure the resin composition of the present invention, but for example, in terms of exposure energy at a wavelength of 365 nm, it is preferably 50 to 10,000 mJ/cm ² , and 200 to 8,000 mJ/cm ² It is more desirable.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, and 240 to 550 nm is preferable.

The exposure wavelength is related to the light source: (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, and i lines), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) , F ₂ excimer laser (wavelength 157 nm), (5) extreme ultraviolet; Examples include EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser's second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferable, and exposure with i-line is especially preferable. Thereby, particularly high exposure sensitivity can be obtained.

In addition, the method of exposure is not particularly limited, and any method is sufficient as long as at least a part of the film made of the resin composition of the present invention is exposed, and examples include exposure using a photomask and exposure using a laser direct imaging method.

<Heating process after exposure>

The film may be subjected to a heating process after exposure (post-exposure heating process).

That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step.

The post-exposure heating process can be performed after the exposure process and before the development process.

The heating temperature in the post-exposure heating process is preferably 50°C to 140°C, and more preferably 60°C to 120°C.

The heating time in the post-exposure heating process is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes.

The temperature increase rate in the post-exposure heating process is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature.

Additionally, the temperature increase rate may be appropriately changed during heating.

The heating means in the post-exposure heating process is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used.

Additionally, it is also preferable to carry out the heating in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.

<Development process>

The film after exposure may be subjected to a development process in which a pattern is formed by developing using a developing solution.

That is, the method for producing a cured product of the present invention may include a development step in which the film exposed through the exposure step is developed using a developer to form a pattern. By performing development, either the exposed portion or the non-exposed portion of the film is removed, thereby forming a pattern.

Here, the phenomenon in which the non-exposed portion of the film is removed by the developing process is called a negative phenomenon, and the phenomenon in which the exposed portion of the film is removed by the developing process is called a positive phenomenon.

〔developer〕

Examples of the developer used in the development process include an aqueous alkaline solution or a developer containing an organic solvent.

When the developing solution is an aqueous alkaline solution, basic compounds that the aqueous alkaline solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, and TMAH (tetrahydroxide Methylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldimethylamine Ethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium Hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide Oxides, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. For example, when using TMAH, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.3 to 3% by mass of the total mass of the developer. .

When the developer contains an organic solvent, the organic solvent is esters, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and beauty. Ethyl lactate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxyacetic acid) Butyl (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionic acid) Methyl, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid Alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. 2-methoxy- Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. , and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl. Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol Colmonomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, and cyclopentane. cyclohexane, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and limonene. Cyclic terpenes such as sulfoxides, dimethyl sulfoxide, and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, and propylene glycol. , methylisobutylcarbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be suitably mentioned.

When the developing solution contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, A developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. It is particularly preferable that it is above. Moreover, the said content may be 100 mass %.

The developing solution may further contain other components.

Other components include, for example, known surfactants and known antifoaming agents.

[How to supply developer]

The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, including a method of immersing the substrate on which the film is formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or continuous application of the developer. There is a way to supply it. There is no particular limitation on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles.

From the viewpoint of penetrability of the developer, removability of non-image areas, and manufacturing efficiency, it is preferable to supply the developer with a straight nozzle or continuously with a spray nozzle. From the viewpoint of the permeability of the developer to the image area, spray A method of supplying through a nozzle is more preferable.

Alternatively, a process may be adopted in which the developer is continuously supplied through a straight nozzle, then the substrate is spun to remove the developer from the substrate, and after spin-drying, the developer is continuously supplied again through a straight nozzle, and then the substrate is spun to remove the developer from the substrate. , this process may be repeated multiple times.

In addition, methods for supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is maintained in a substantially stationary state on the substrate, a process in which the developer is vibrated on the substrate by ultrasonic waves, etc., and a process combining them. etc. are available for employment.

As developing time, 10 seconds to 10 minutes is preferable, and 20 seconds to 5 minutes is more preferable. The temperature of the developing solution during development is not particularly determined, but is preferably 10 to 45°C, more preferably 18 to 30°C.

In the development process, after treatment using a developing solution, the pattern may be further cleaned (rinsed) with a rinsing solution. Additionally, a method such as supplying a rinse solution while the developer in contact with the pattern is not completely dried may be adopted.

[Rinse liquid]

When the developing solution is an aqueous alkaline solution, water can be used as the rinsing solution, for example. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid. there is.

When the rinse liquid contains an organic solvent, examples of the organic solvent include esters, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, alkyloxy acetate) Butyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxy Methyl propionate, 3-alkyloxy ethyl propionate, etc. (e.g., 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.), 2-alkyloxy Alkyl propionic acid esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-meth Propyl oxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g. 2-methoxy -2-methylpropionate, 2-ethoxy-2-methylethylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol Lycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclohexanone, etc. Pentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, Cyclic terpenes such as limonene, dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, and propylene glycol as alcohols. , methylisobutylcarbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can be suitably mentioned.

When the rinse liquid contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, and cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide are particularly preferred. Side, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are more preferred.

When the rinse liquid contains an organic solvent, 50% by mass or more of the rinse liquid is preferably an organic solvent, more preferably 70% by mass or more is an organic solvent, and more preferably 90% by mass or more is an organic solvent. do. Additionally, 100% by mass of the rinse liquid may be an organic solvent.

The rinse liquid may further contain other ingredients.

Other components include, for example, known surfactants and known antifoaming agents.

[How to supply rinse liquid]

The method of supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by spreading the liquid, and supplying the rinse liquid to the substrate by showering. There is a method of continuously supplying the rinse liquid onto the substrate using means such as a straight nozzle.

From the viewpoints of the permeability of the rinse solution, removability of the non-burn area, and manufacturing efficiency, there are methods of supplying the rinse solution to shower nozzles, straight nozzles, spray nozzles, etc., and a method of continuously supplying the rinse solution to the spray nozzle is preferable, and the method of supplying the rinse solution to the burn area is preferred. From the viewpoint of the permeability of the rinse liquid to water, the method of supplying it through a spray nozzle is more preferable. There is no particular limitation on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles.

That is, the rinsing process is preferably a process of supplying the rinse solution to the film after exposure through a straight nozzle or continuously, and more preferably is a process of supplying the rinse solution via a spray nozzle.

In addition, the method of supplying the rinse liquid in the rinse process includes a process in which the rinse liquid is continuously supplied to the substrate, a process in which the rinse liquid is maintained in a substantially stationary state on the substrate, a process in which the rinse liquid is vibrated on the substrate by ultrasonic waves, etc., and Processes that combine them can be adopted.

As a rinse time, 10 seconds to 10 minutes is preferable, and 20 seconds to 5 minutes is more preferable. The temperature of the rinse liquid during rinsing is not particularly determined, but is preferably 10 to 45°C, more preferably 18 to 30°C.

<Heating process>

The pattern obtained through the development process (if a rinsing process is performed, the pattern after rinsing) may be subjected to a heating process in which the pattern obtained through the development process is heated.

That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained through the development step.

Additionally, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained by a film forming step.

In the heating process, resin such as polyimide precursor is cyclized to become resin such as polyimide.

In addition, crosslinking of unreacted crosslinkable groups in the specific resin or crosslinking agent other than the specific resin also proceeds.

The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, more preferably 150 to 250°C, even more preferably 160 to 250°C, and 160°C. ~230°C is particularly preferred.

The heating process is preferably a process of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and the action of a base or the like generated from the base generator.

Heating in the heating process is preferably performed at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C/min, and more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of acids or solvents can be prevented while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, residual stress in the cured product can be alleviated.

Additionally, in the case of an oven capable of rapid heating, it is preferable to perform the temperature increase at a rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec. desirable.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and still more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after this drying is, for example, 30 to 30% higher than the boiling point of the solvent contained in the resin composition of the present invention. It is desirable to raise the temperature from a temperature as low as 200°C.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

Especially when forming a multi-layer laminate, from the viewpoint of adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and especially preferably 120°C or higher. .

The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating may be performed in stages. For example, a process such as raising the temperature from 25℃ to 120℃ at 3℃/min, holding at 120℃ for 60 minutes, raising the temperature at 2℃/min from 120℃ to 180℃, and holding at 180℃ for 120 minutes. You can do it. Additionally, it is also preferable to process while irradiating ultraviolet rays as described in U.S. Patent Publication No. 9159547. It is possible to improve the properties of the membrane through this pretreatment process. The pretreatment process may be performed for a short period of time, such as 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferable. The pretreatment may be performed in two or more steps, for example, the first stage pretreatment process may be performed in the range of 100 to 150°C, and then the second stage pretreatment process may be performed in the range of 150 to 200°C.

Additionally, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

The heating process is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or by performing it under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

The heating means in the heating process is not particularly limited, and examples include a hot plate, an infrared furnace, an electric heat oven, a hot air oven, and an infrared oven.

<Exposure process after development>

The pattern obtained by the developing process (if a rinsing process is performed, the pattern after rinsing) may be subjected to a post-development exposure process that exposes the pattern after the developing process instead of or in addition to the heating process.

That is, the method for producing a cured product of the present invention may include a post-development exposure process for exposing the pattern obtained through the development process. The method for producing a cured product of the present invention may include a heating process and a post-development exposure process, or may include only one of the heating process and a post-development exposure process.

In the exposure process after development, for example, a reaction in which cyclization of a polyimide precursor, etc. proceeds by sensitization of a photobase generator, a reaction in which desorption of an acid-decomposable group proceeds by sensitization of a photoacid generator, etc. are promoted. You can do it.

In the post-development exposure process, at least part of the pattern obtained in the development process may be exposed, but it is preferable that the entire pattern is exposed.

The exposure amount in the exposure step after development is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.

The exposure process after development can be performed, for example, using the light source in the exposure process described above, and it is preferable to use broadband light.

<Metal layer formation process>

The pattern obtained through the development process (preferably provided in at least one of the heating process and the post-development exposure process) may be applied to the metal layer forming process of forming a metal layer on the pattern.

That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development process (preferably provided in at least one of the heating process and the post-development exposure process).

As the metal layer, there is no particular limitation, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, and copper and Aluminum is more preferred, and copper is still more preferred.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent Publication No. 7888181B2, US Patent Publication No. The method described in 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. A preferable mode of plating includes electrolytic plating using copper sulfate or copper cyanide plating solution.

The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm in the thickest part.

<Use>

Fields to which the method for producing the cured product of the present invention or the cured product of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, patterns may be formed by etching sealing films, substrate materials (base films, cover lays, and interlayer insulating films of flexible printed circuit boards), or insulating films for packaging purposes as described above. Regarding these uses, for example, Science & Technology Co., Ltd. "High-performance polyimide and application technology", April 2008, Masaaki Kakimoto/supervision, CMC Technical Library "Basics and development of polyimide materials", 2011, 11 You can refer to the Japanese Polyimide and Aromatic Polymer Research Society/edit, “Latest Polyimide Basics and Applications,” N·T·S, August 2010, published in January.

In addition, the method for producing the cured product of the present invention, or the cured product of the present invention, can be used in the production of plate surfaces such as offset plates or screen plates, for use in etching of molded parts, as a protective lacquer in electronics, especially microelectronics, and It can also be used for manufacturing dielectric layers, etc.

(Laminate and method for manufacturing the laminate)

The laminate of the present invention refers to a structure having a plurality of layers made of the cured material of the present invention.

The laminate of the present invention is a laminate containing two or more layers of cured material, and may be a laminate in which three or more layers are laminated.

Among the two or more layers of the cured material included in the laminate, at least one is a layer of the cured material of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the shrinkage, It is also preferable that all the layers made of the cured material contained in the above-described laminate are made of the cured material of the present invention.

That is, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured material, and includes a metal layer between any one of the layers made of the cured material. The metal layer is preferably formed by the metal layer forming process.

That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product performed multiple times. The preferred embodiment of the metal layer forming process is as described above.

As the above-mentioned laminate, for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured material, a metal layer, and a layer made of the second cured material are laminated in this order can be cited as a preferable one. .

It is preferable that the layer made of the first cured material and the layer made of the second cured material are both layers made of the cured material of the present invention. The resin composition of the present invention used to form a layer made of the first cured material and the resin composition of the present invention used to form a layer made of the second cured material may have the same composition or may have different compositions. It may be a composition. The metal layer in the laminate of the present invention is preferably used as a metal wiring such as a redistribution layer.

<Laminating process>

The manufacturing method of the laminated body of the present invention preferably includes a lamination process.

The lamination process refers to (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and post-development exposure again on the surface of the pattern (resin layer) or metal layer. It is a series of processes including performing one of the processes in this order. However, at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated. Moreover, (e) a metal layer formation process may be included after at least one of the (d) heating process and the post-development exposure process. It goes without saying that the lamination process may further include the above drying process, etc. as appropriate.

When performing an additional lamination process after the lamination process, a surface activation treatment process may be further performed after the exposure process, the heating process, or the metal layer formation process. An example of surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.

The lamination process is preferably performed 2 to 20 times, and is more preferably performed 2 to 9 times.

For example, a configuration in which the resin layer is 2 to 20 layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferable, and a configuration in which the resin layer is 2 to 9 layers is more preferable. .

The composition, shape, film thickness, etc. of each of the above layers may be the same or different.

In the present invention, it is particularly preferred that, after providing the metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, (a) a film formation process, (b) an exposure process, (c) a development process, (d) at least one of a heating process and a post-development exposure process, (e) a metal layer formation process is repeated in this order, Alternatively, an aspect in which at least one of (a) the film formation process, (d) the heating process and the post-development exposure process, and (e) the metal layer formation process are repeated in this order can be mentioned. By alternately performing the lamination process of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming process, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment process)

The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.

The surface activation treatment process is usually performed after the metal layer formation process, but after the development process (preferably after at least one of the heating process and the post-development exposure process), the surface activation treatment process is performed on the resin composition layer, A metal layer forming step may be performed.

The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, or may be performed on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least part of the metal layer, and the surface activation treatment is preferably performed on part or all of the area where the resin composition layer is formed on the surface of the metal layer. In this way, by performing surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved.

In addition, the surface activation treatment is preferably performed on part or all of the resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the resin composition layer, adhesion to the metal layer or resin layer provided on the surface that has been subjected to the surface activation treatment can be improved. In particular, when the resin composition layer is cured, such as when performing negative development, it is difficult to receive damage from surface treatment, and adhesion is likely to improve.

As surface activation treatment, specifically, plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O ₂ , SF ₆ , NF ₃ , NF ₃ After etching treatment with /O ₂ , surface treatment with ultraviolet (UV) ozone method, and immersion in an aqueous hydrochloric acid solution to remove the oxide film, it has at least one amino group and one thiol group. It is selected from immersion treatment in an organic surface treatment agent containing a compound and mechanical roughening treatment using a brush, and plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/m ² , more preferably 1000 to 100,000 J/m ² , and most preferably 10,000 to 50,000 J/m ² .

(Semiconductor device and manufacturing method thereof)

The present invention also discloses a semiconductor device containing the cured product of the present invention or the laminate of the present invention.

Additionally, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate of the present invention. As a specific example of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a redistribution layer, the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. It is used in the specification.

Example

The present invention will be described in more detail below with reference to examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. “Part” and “%” are based on mass, unless otherwise specified.

<Synthesis of Compound B>

[Synthesis of SA-1]

In a flask equipped with a stirrer and condenser, 13.0 g (100 mmol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.001 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.01 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was dissolved in 60 mL of tetrahydrofuran, and stirred at 25°C. Next, 11.9 g (100 mmol) of phenyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 1 hour, the temperature was raised to 50°C, and the mixture was stirred for 4 hours. Subsequently, this was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, it was washed in that order with diluted hydrochloric acid, sodium bicarbonate, and saturated saline solution, and the solvent was removed with an evaporator to obtain 18 g of SA-1. SA-1 is presumed to be a compound represented by the following formula SA-1. It was confirmed that it was SA-1 from ¹ H-NMR spectrum.

[Synthesis of SA-2 to SA-22]

In the synthesis of SA-1, SA-2 was produced by the same method as the synthesis of SA-1, except that the alcohol (2-hydroxyethyl methacrylate) and isocyanate (phenyl isocyanate) were changed. ~SA-22 was synthesized. SA-2 to SA-22 are presumed to be compounds represented by the following formulas SA-2 to SA-22, respectively.

[Synthesis of SA-23]

In a flask equipped with a stirrer and condenser, 5.36 g (50 mmol) of N-methylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 4.51 g (55 mmol) of N-methylimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) ), 0.001 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 80 mL of chloroform, and stirred at 10 to 20°C. Next, 9.77 g (52.5 mmol) of diallyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and then stirred at 10 to 20°C for 5 hours. Subsequently, it was transferred to a separatory funnel while adding 300 mL of chloroform, washed in that order with diluted hydrochloric acid, sodium bicarbonate, and saturated saline solution, and the solvent was removed with an evaporator to obtain 7.2 g of SA-23. SA-23 is presumed to be a compound represented by the following formula SA-23. It was confirmed that it was SA-23 from ¹ H-NMR spectrum.

[Synthesis of SA-24 to SA-25]

SA-24 to SA-25 were synthesized by the same method as SA-23, except that the raw material compounds were changed appropriately. SA-24 to SA-25 are presumed to be compounds represented by the following formulas SA-24 to SA-25, respectively.

[Formula 65]

[Formula 66]

<Synthesis Example A-1: Synthesis of polyimide precursor (A-1)>

21.2 g (68.1 mmol) of 4,4'-oxydiphthalic dianhydride, 17.8 g (137 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 22.8 g (289 mmol) of Pyridine and 85 g of diglyme were mixed and stirred at a temperature of 60°C for 6 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the mixture was cooled to -20°C, and then 16.7 g (140 mmol) of thionyl chloride was added dropwise over 90 minutes and stirred for 2 hours, and a white precipitate of pyridinium hydrochloride was obtained. Next, 21.1 g (57.2 mmol) of 4,4'-bis(4-aminophenoxy)biphenyl dissolved in 100 mL of NMP was added dropwise over 1 hour. Next, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain a polyimide precursor (A-1). The weight average molecular weight of the obtained polyimide precursor A-1 was 18,100 and the number average molecular weight was 8,400.

The structure of A-1 is assumed to be a structure represented by the following formula (A-1).

[Formula 67]

<Synthesis Example A-2: Synthesis of polyimide precursor (A-2)>

10.6 g (34.1 mmol) of 4,4'-oxydiphthalic dianhydride, 10.0 g (34 mmol) of 4,4'-biphthalic dianhydride, and 17.8 g (137 mmol) of 2-hydroxyethylmethane. Crylate, 0.05 g of hydroquinone, 22.8 g (289 mmol) of pyridine, and 85 g of diglyme were mixed, stirred at a temperature of 60°C for 6 hours, and 4,4'-oxydiphthalic acid and 2 -A diester of hydroxyethyl methacrylate was prepared. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-bis(4-aminophenoxy)biphenyl in the same manner as Synthesis Example A-1, and Synthesis Example A Polyimide precursor (A-2) was obtained in the same manner as -1. The weight average molecular weight of this polyimide precursor was 17,600, and the number average molecular weight was 7,800. The structure of A-2 is assumed to be a structure represented by the following formula (A-2).

[Formula 68]

<Synthesis Example A-3: Synthesis of polyimide precursor (A-3)>

[Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: Polyimide precursor with radical polymerizable group) ) synthesis]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinol. Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60°C for 18 hours to form a mixture of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The ester was prepared. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5. The polyimide precursor (A-3) was obtained. The weight average molecular weight of this polyimide precursor was 19,600.

The structure of A-3 is assumed to be a structure represented by the following formula (A-3).

[Formula 69]

<Synthesis Example A-4: Synthesis of polyimide precursor (A-4)>

[Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine) and 2-hydroxyethyl methacrylate (A -4: Synthesis of polyimide precursor having a radical polymerizable group)]

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinol. Rice paddy, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60°C for 18 hours to form a mixture of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The ester was prepared. Next, the obtained diester was chlorinated with SOCl ₂ and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as Synthesis Example A-5, and synthesized in Synthesis Example A polyimide precursor (A-4) was obtained in the same manner as A-5. The weight average molecular weight of this polyimide precursor was 23,500.

The structure of A-4 is assumed to be a structure represented by the following formula (A-4).

[Formula 70]

<Synthesis Example A-5: Synthesis of polyimide precursor (A-5)>

[A-5: Polyimide precursor resin A-5 from oxydiphthalic dianhydride, 4,4'-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether synthesis〕

While removing moisture in a dry reactor equipped with a flat-bottom joint equipped with a stirrer, condenser, and internal thermometer, 9.49 g (32.25 mmol) of 4,4'-biphthalic anhydride and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were added. ) was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were continuously added, and stirred at a temperature of 60°C for 18 hours. Next, the mixture was cooled to -20°C, and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent solution. Next, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain a polyimide precursor (A-5). The weight average molecular weight of the obtained polyimide precursor A-5 was 23,800 and the number average molecular weight was 10,400.

The structure of A-5 is assumed to be a structure represented by the following formula (A-5).

[Formula 71]

<Synthesis Example A-6>

[A-6: Polyimide precursor from 4,4'-oxydiphthalic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-6: radical polymerizable group) [Synthesis of polyimide precursor)]

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After completion of heat generation due to the reaction, the mixture was allowed to cool to room temperature and left to stand for an additional 16 hours.

Next, under ice cooling, a solution in which 206.3 g of dicyclohexylcarbodiimide (DCC) was dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes while stirring. Subsequently, a suspension in which 93.0 g of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone was added while stirring for 60 minutes. After stirring at room temperature for an additional 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. After that, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was collected by filtration to obtain a reaction solution.

The obtained reaction liquid was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and dried under vacuum to obtain powdery polymer A-6. The weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 24,000.

<Synthesis Example A-7>

[Polyimide precursor from 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (A-7: radical Synthesis of polyimide precursor having a polymerizable group]

In Synthesis Example A-6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride. Polymer A-7 was obtained by carrying out the reaction in the same manner as described. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900.

<Synthesis Example A-8>

In a flask equipped with a stirrer and condenser, 19.19 g (36.7 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 4-meth 0.01 g of toxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 21.98 g (75 mmol) of CS-1 (the above synthetic product), 12.92 g (163 mmol) of pyridine, diethylene glycol dimethyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) It was mixed with 40.0 g of Co., Ltd. and stirred at a temperature of 60°C for 6 hours. Next, the mixture was cooled to -20°C, and then 9.19 g (76.3 mmol) of thionyl chloride was added dropwise over 90 minutes and stirred for 2 hours. Next, 25 mL of N-methylpyrrolidone (NMP) was added, and 6.11 g (30.5 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 2 hours. Next, 16.9 g (367 mmol) of ethanol was added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor resin was dried at 45°C for 2 days under reduced pressure to obtain a polyimide precursor (A-8). The weight average molecular weight of the obtained polyimide precursor A-8 was 30,100 and the number average molecular weight was 13,800.

The structure of A-8 is assumed to be a structure represented by the following formula (A-8).

[Formula 72]

<Synthesis Example A-9: Synthesis of polyimide>

In a flask equipped with a condenser and a stirrer, while removing moisture, 26.0 g of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 50 mmol), 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 120.0 g of N-methylpyrrolidone (NMP). Next, 11.9 g (45 mmol) of diamine (AA-1) described later was added, and the mixture was stirred at 25°C for 3 hours and stirred at 45°C for an additional 3 hours. Next, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and N-methylpyrrolidone (NMP) was added. ) 50g was added and diluted.

This reaction solution was precipitated in 1 liter of methanol and stirred at a speed of 3000 rpm for 15 minutes. The resin was removed by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure to obtain polyimide A-9. The molecular weight of A-9 was Mw = 21,000 and Mn = 9,100.

The structure of polyimide A-9 is assumed to be a structure represented by the following formula (A-9).

[Formula 73]

[Synthesis Example AA-1: Synthesis of diamine AA-1]

In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 17.4 g (0.2 mol) of dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) g (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5°C or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added dropwise into the flask over 1 hour using a dropping funnel. did. After the dropwise addition was completed, the mixture was stirred at 10°C or lower for 30 minutes, the temperature was raised to 25°C, and the mixture was stirred for 3 hours. Next, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed sequentially with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline solution. . After liquid separation and washing, it was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and dried under vacuum to obtain 61.0 g of dinitrobody (A-1).

In a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and acetic acid. Weigh 3.0 g (50 mmol) of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.03 g (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). , 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.

Next, 16.2 g of the dinitrobody (A-1) was added in small amounts for 1 hour and stirred for 30 minutes. Next, the external temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or lower, and then filtered using Celite (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate water, followed by sequential washing with 300 mL of water and 300 mL of saturated saline solution. After liquid separation and washing, it was dried with 30 g of magnesium sulfate, concentrated using an evaporator, and dried under vacuum to obtain 11.0 g of diamine (AA-1).

[Formula 74]

<Synthesis of comparative compound Cmp-1>

In a flask equipped with a stirrer and condenser, 10.2 g (100 mmol) of 1-hexanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.001 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and Neostan U-600. 0.01 g (manufactured by Nitto Kasei Co., Ltd.) was dissolved in 60 mL of tetrahydrofuran and stirred at 25°C. Next, 11.9 g (100 mmol) of phenyl isocyanate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 1 hour, the temperature was raised to 50°C, and the mixture was stirred for 4 hours. Subsequently, this was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, it was washed in that order with diluted hydrochloric acid, sodium bicarbonate, and saturated saline solution, and the solvent was removed with an evaporator to obtain 15 g of Cmp-1. The structure of Cmp-1 is assumed to be the structure represented by the following formula (Cmp-1). It was confirmed that it was Cmp-1 from ¹ H-NMR spectrum.

[Formula 75]

<Synthesis of comparative compound Cmp-2>

In a flask equipped with a stirrer and condenser, 10.2 g (100 mmol) of 1-hexanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.001 g of p-methoxyphenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and Neostan U- 0.01 g of 600 (manufactured by Nitto Kasei Co., Ltd.) was dissolved in 80 mL of tetrahydrofuran and stirred at 25°C. Next, 15.5 g (100 mmol) of Karenz MOI (manufactured by Showa Denko Co., Ltd.) was added dropwise over 1 hour, then the temperature was raised to 50°C and stirred for 4 hours. Subsequently, this was dissolved in 800 mL of ethyl acetate and transferred to a separatory funnel. Subsequently, it was washed in that order with diluted hydrochloric acid, sodium bicarbonate, and saturated saline solution, and the solvent was removed with an evaporator to obtain 19.5 g of Cmp-2. The structure of Cmp-2 is assumed to be a structure represented by the following formula (Cmp-2). It was confirmed from ¹ H-NMR spectrum that it was Cmp-2.

[Formula 76]

<Examples and Comparative Examples>

In each example, the components listed in the table below were mixed to obtain each resin composition. In addition, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.

Specifically, the content of each component described in the table was set to the amount (parts by mass) described in the “Amount added” column in each column of the table.

The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a micropore width of 0.5 μm.

In addition, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

[Table 1]

[Table 2]

The details of each component listed in the table are as follows.

[Resin (cyclized resin or its precursor)]

·A-1~A-9: A-1~A-9 synthesized above

[Compound B or comparative compound]

SA-1 to SA-25: The above synthetic product (Compound B)

·Cmp-1: The above synthetic product (comparative compound)

·Cmp-2: The above synthetic product (comparative compound)

[Polymerization initiator (all brand names)]

・OXE-01: IRGACURE OXE 01 (manufactured by BASF)

・OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Base generator]

·D-1 to D-2: Compounds with the following structure

・D-3: WPBG-027 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[Formula 77]

[Migration inhibitor]

·E-1 to E-6: Compounds with the following structure

[Formula 78]

[Metal adhesion improver]

·F-1 to F-3: Compounds with the following structure

[Formula 79]

[Polymerizable compounds (all brand names)]

SR-209: SR-209 (manufactured by Sartomer)

SR-231: SR-231 (manufactured by Sartomer)

DPE-400: Blemmer DPE-400 (manufactured by Nichiyu Co., Ltd.)

ADPH: Dipentaerythritol hexaacrylate (manufactured by Shinnakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]

·H-1: 1,4-benzoquinone

·H-2: 4-methoxyphenol

·H-3: 1,4-dihydroxybenzene

·H-4: Compound with the following structure

[Formula 80]

[Other additives]

I-1: N-phenyldiethanolamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

〔solvent〕

DMSO: dimethyl sulfoxide

·GBL: γ-Beautyrolactone

·NMP: N-methylpyrrolidone

In the table, the description “DMSO/GBL” indicates that DMSO and GBL were mixed at a mixing ratio (mass ratio) of DMSO:GBL=80:20.

<Evaluation>

[Evaluation of breaking elongation]

In each Example and Comparative Example, the resin composition or comparative composition was applied on a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer with a uniform thickness of about 15 μm on the silicon wafer.

The entire surface of the obtained resin composition layer was subjected to i-line exposure with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C).

The resin composition layer (resin layer) after the exposure was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, and was heated for 3 hours after reaching the temperature described in the “Temperature” column of “Curing Conditions” in the table. The cured resin layer (cured film) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured film was peeled from the silicon wafer. The peeled cured film was punched using a punching machine to produce a test piece with a sample width of 3 mm and a sample length of 30 mm. The obtained test piece was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, in an environment of 25°C and 65%RH (relative humidity), and the breaking elongation in the longitudinal direction of the test piece was measured in accordance with JIS-K6251. Measured. The evaluation was performed five times each, and the arithmetic mean value of the elongation rate (elongation at break) when the test piece broke was used as a reference value.

The above-described reference values were evaluated according to the following evaluation criteria, and the evaluation results were described in the "breaking elongation" column of the table. It can be said that the larger the above-mentioned index value, the better the film strength (elongation at break) of the obtained cured film.

(Evaluation standard)

A: The above indicator value was 60% or more.

B: The above indicator value was 55% or more and less than 60%.

C: The above indicator value was 50% or more and less than 55%.

D: The above indicator value was less than 50%.

[Evaluation of chemical resistance]

Each resin composition or comparative composition prepared in each Example and Comparative Example was applied to a silicon wafer by spin coating, respectively, to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The entire resin composition layer on the silicon wafer was exposed to exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed resin composition layer (resin layer) was heated at 10°C/min under a nitrogen atmosphere. The temperature was raised at a temperature increase rate of minutes and heated for 180 minutes at the temperature described in the "Temperature" column of "Curing Conditions" in the table to obtain a cured layer (resin layer) of the resin composition layer.

The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.

Chemical solution: 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution.

Evaluation conditions: The resin layer was immersed in a chemical solution at 75°C for 15 minutes, the film thickness before and after immersion was compared, and the dissolution rate (nm/min) was calculated. The film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22, manufactured by Foothill) and obtained as the arithmetic mean value.

Evaluation was conducted according to the following evaluation criteria, and the evaluation results were described in the "Chemical Resistance" column of the table. It can be said that the lower the dissolution rate, the better the chemical resistance.

-Evaluation standard-

A: The dissolution rate was less than 200 nm/min.

B: The dissolution rate was 200 nm/min or more and less than 300 nm/min.

C: The dissolution rate was 300 nm/min or more and less than 400 nm/min.

D: The dissolution rate was 400 nm/min or more.

[Evaluation of internal stress]

Evaluation of internal stress was performed as follows.

Each resin composition or comparative composition prepared in each Example and Comparative Example was applied to a 12-inch silicon wafer by spin coating, respectively, to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The entire resin composition layer on the silicon wafer was exposed to exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed resin composition layer (resin layer) was heated at 10°C/min under a nitrogen atmosphere. The temperature was raised at a temperature increase rate of minutes and heated for 180 minutes at the temperature described in the "Temperature" column of "Curing Conditions" in the table to obtain a cured layer (resin layer) of the resin composition layer. 24 hours after the end of the 180-minute heating process, the amount of warpage of the wafer was measured, and the internal stress was calculated from the following equation.

Radius of curvature ρ=length of substrate L ² /8ξ+ξ/2

L: Length of substrate (12 inches, 1 inch = 2.54 cm)

ξ: Deflection amount

Internal stress=E ₁ ×h ₁ ³ /12h ₂ ×2/ρ(h ₁ +h ₂ )×[1+1/3{h ₁ /(h ₁ +h ₂ )} ² ]

E ₁ : elastic modulus of the substrate (MPa)

h ₁ : Thickness of substrate (775μm)

h ₂ : Thickness of cured film after curing (measured by ellipsometer)

The elastic modulus of the substrate was calculated by the method described in JIS (Japanese Industrial Standard) K 7171:2016.

Evaluation was performed according to the following evaluation criteria, and the evaluation results were described in the "Internal Stress" column of the table. The smaller the internal stress, the smaller the warpage of the wafer, which can be said to be excellent.

-Evaluation standard-

A: The internal stress was less than 20 mPa.

B: The internal stress was 20 mPa or more and less than 25 mPa.

C: The internal stress was 25 mPa or more and less than 30 mPa.

D: Internal stress was 30 mP or more.

From the above results, it can be seen that the cured film made of the resin composition according to the present invention has excellent chemical resistance.

The comparative compositions of Comparative Examples 1 to 3 do not contain compound B.

It can be seen that the cured film made of such a comparative composition is inferior in chemical resistance.

<Example 101>

The resin composition used in Example 1 was applied in a layered manner to the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed by spin coating, dried at 100°C for 4 minutes, and a resin composition layer with a film thickness of 20 μm was formed. After formation, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 μm). After exposure, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.

Next, in a nitrogen atmosphere, the temperature was raised at a temperature increase rate of 10°C/min, and after reaching 230°C, the temperature was maintained at 230°C for 3 hours to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for the redistribution layer had excellent insulating properties.

Additionally, as a result of manufacturing a semiconductor device using the interlayer insulating film for the redistribution layer, it was confirmed that it operated without problems.

Claims (16)

Cyclized resin or a resin that is its precursor, and
A resin composition containing compound B represented by formula (1-1).
[Formula 1]

X ¹ represents an n-valent ^linking group containing an aromatic ring structure, at least ^one of the bonding sites with the nitrogen atom in the formula for represents a group ^, R ¹ may ^{combine with} represents an integer of 1 or more, and m represents an integer of 1 or more. In claim 1,
A resin composition wherein the content of the compound B relative to the total mass of the resin composition is 1% by mass or more. In claim 1 or claim 2,
A resin composition further comprising a polymerizable compound different from the compound B. In claim 3,
A resin composition wherein the content of the polymerizable compound is more than 0% by mass and 20% by mass or less, based on the total mass of the composition. The method according to any one of claims 1 to 4,
A resin composition wherein the acid value of the resin is 1 mmol/g or less. The method according to any one of claims 1 to 5,
A resin composition wherein the resin has a polymerizable group. The method according to any one of claims 1 to 6,
A resin composition wherein the molecular weight of the compound B is 1,000 or less. The method according to any one of claims 1 to 7,
A resin composition further comprising a polymerization initiator. The method according to any one of claims 1 to 8,
A resin composition wherein W ¹ in the formula (1-1) is a radical polymerizable group. The method according to any one of claims 1 to 9,
A resin composition used for forming an interlayer insulating film for a redistribution layer. A cured product obtained by curing the resin composition according to any one of claims 1 to 10. A laminate comprising two or more layers made of the cured material according to claim 11, and including a metal layer between any one of the layers made of the cured material. A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of claims 1 to 10 to a substrate to form a film. In claim 13,
A method for producing a cured product, comprising an exposure process of exposing the film and a development process of developing the film. In claim 13 or claim 14,
A method for producing a cured product, comprising a heating process of heating the film at 50 to 450°C. A semiconductor device comprising the cured product according to claim 11 or the laminate according to claim 12.